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甲苯二异氰酸酯向空气中的排放以及从软质聚氨酯泡沫迁移至表面的情况。

Toluene diisocyanate emission to air and migration to a surface from a flexible polyurethane foam.

作者信息

Vangronsveld Erik, Berckmans Steven, Spence Mark

机构信息

Huntsman (Europe) BVBA, Everslaan 45, 3078 Everberg, Belgium.

出版信息

Ann Occup Hyg. 2013 Jun;57(5):650-61. doi: 10.1093/annhyg/mes105. Epub 2013 May 16.

Abstract

Flexible polyurethane foam (FPF) is produced from the reaction of toluene diisocyanate (TDI) and polyols. Because of the potential for respiratory sensitization following exposure to TDI, concerns have been raised about potential consumer exposure to TDI from residual 'free TDI' in FPF products. Limited and conflicting results exist in the literature concerning the presence of unreacted TDI remaining in FPF as determined by various solvent extraction and analysis techniques. Because residual TDI results are most often intended for application in assessment of potential human exposure to TDI from FPF products, testing techniques that more accurately simulated human contact with foam were designed. To represent inhalation exposure to TDI from polyurethane foam, a test that measured the emission of TDI to air was conducted. For simulation of human dermal exposure to TDI from polyurethane foam, a migration test technique was designed. Emission of TDI to air was determined for a representative FPF using three different emission test cells. Two were commercially available cells that employ air flow over the surface of the foam [the Field and Laboratory Emission Cell (FLEC®) and the Micro-Chamber/Thermal Extraction™ cell]. The third emission test cell was of a custom design and features air flow through the foam sample rather than over the foam surface. Emitted TDI in the air of the test cells was trapped using glass fiber filters coated with 1-(2-methoxyphenyl)-piperazine (MP), a commonly used derivatizing agent for diisocyanates. The filters were subsequently desorbed and analyzed by liquid chromatography/mass spectrometry. Measurement of TDI migration from representative foam was accomplished by placing glass fiber filters coated with MP on the outer surfaces of a foam disk and then compressing the filters against the disk using a clamping apparatus for periods of 8 and 24 h. The sample filters were subsequently desorbed and analyzed in the same manner as for the emission tests. Although the foam tested had detectable levels of solvent-extractable TDI (56ng TDI g(-1) foam for the foam used in emissions tests; 240-2800ng TDI g(-1) foam for the foam used in migration tests), no TDI was detected in any of the emission or migration tests. Method detection limits (MDLs) for the emissions tests ranged from 0.03 to 0.5ng TDI g(-1) foam (0.002-0.04ng TDI cm(-2) of foam surface), whereas those for the migration tests were 0.73ng TDI g(-1) foam (0.16ng TDI cm(-2) of foam surface). Of the three emission test methods used, the FLEC® had the lowest relative MDLs (by a factor of 3-10) by virtue of its high chamber loading factor. In addition, the FLEC® cell offers well-established conformity with emission testing standard methods.

摘要

软质聚氨酯泡沫(FPF)由甲苯二异氰酸酯(TDI)与多元醇反应制得。由于接触TDI后存在呼吸道致敏的可能性,人们对消费者通过FPF产品中残留的“游离TDI”接触TDI的潜在风险表示担忧。关于通过各种溶剂萃取和分析技术测定的FPF中未反应TDI的存在情况,文献中的结果有限且相互矛盾。由于残留TDI的结果通常用于评估人类通过FPF产品接触TDI的潜在风险,因此设计了能更准确模拟人类与泡沫接触情况的测试技术。为了表示从聚氨酯泡沫中吸入TDI的情况,进行了一项测量TDI向空气中排放的测试。为了模拟人类通过聚氨酯泡沫进行皮肤接触TDI的情况,设计了一种迁移测试技术。使用三种不同的排放测试池测定了代表性FPF向空气中排放TDI的情况。其中两种是市售的测试池,它们通过在泡沫表面流动空气来进行测试[现场和实验室排放池(FLEC®)以及微室/热萃取™池]。第三个排放测试池是定制设计,其特点是空气流经泡沫样品而非泡沫表面。测试池中空气中排放的TDI使用涂有1-(2-甲氧基苯基)-哌嗪(MP)的玻璃纤维滤膜进行捕集,MP是一种常用的二异氰酸酯衍生化剂。随后对滤膜进行解吸,并通过液相色谱/质谱法进行分析。通过将涂有MP的玻璃纤维滤膜放置在泡沫圆盘的外表面,然后使用夹紧装置将滤膜压在圆盘上8小时和24小时,完成了从代表性泡沫中TDI迁移的测量。随后对样品滤膜进行解吸,并以与排放测试相同的方式进行分析。尽管测试的泡沫具有可检测水平的溶剂可萃取TDI(排放测试中使用的泡沫为56 ng TDI g⁻¹泡沫;迁移测试中使用的泡沫为240 - 2800 ng TDI g⁻¹泡沫),但在任何排放或迁移测试中均未检测到TDI。排放测试的方法检测限(MDL)范围为0.03至0.5 ng TDI g⁻¹泡沫(0.002 - 0.04 ng TDI cm⁻²泡沫表面),而迁移测试的方法检测限为0.73 ng TDI g⁻¹泡沫(0.16 ng TDI cm⁻²泡沫表面)。在所使用的三种排放测试方法中,FLEC®凭借其高腔室负载因子具有最低的相对MDL(低3 - 10倍)。此外,FLEC®池与排放测试标准方法具有良好的一致性。

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