Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, F-63000 Clermont-Ferrand, France.
Laboratory of Analysis of Organic Compounds (509), Faculty of Sciences I, Lebanese University, Hadath, Beirut, Lebanon.
Chemosphere. 2018 Nov;211:943-951. doi: 10.1016/j.chemosphere.2018.07.147. Epub 2018 Jul 30.
Brominated flame retardants (BFRs) are widely used as additives in plastics, textiles and electronics materials. Here, we investigated the photodegradation of four BFRs including decabromobiphenylether (BDE-209), tetrabromobipsphenol A (TBBPA), tetrabromobisphenol A-bis(2,3-dibromopropylether) (TBBPA-DBPE) and tetrabromobisphenol A bis (allyl) ether (TBBPA-BAE). Experiments were carried out in polystyrene (PS) films using monochromatic and polychromatic irradiations. For comparison, irradiations were also carried in a solvent (tetrahydrofuran: THF). Monitoring of BFR degradation was performed using bulk and surface infrared (IR) measurements, as well as by extraction and HPLC-UV. Photoproducts were characterized using HPLC-high resolution electrospray ionization mass spectrometry (HPLC-ESI-Orbitrap-MS). All four BFRs underwent photochemical transformation in THF at 290 nm with a quantum yield (Φ) ranging from 0.05 for TBBPA to 0.27 for BDE-209, indicating an increase of photoreactivity with the number of Br atoms in BFRs. On the other hand, no major difference in the Φ values was observed when BFRs were embedded in PS films (Φ: 0.82-0.89). The higher photoreactivity in PS appears to be associated with a fast oxidation of PS as revealed by infrared (IR) analysis and yellowing of the films. Interestingly, the faster the yellowing occurred, the faster the BFR degradation was inhibited due to light screening effect. Several major photoproducts were identified for TBBPA and TBBPA-DBPE. Additional photoproducts possibly arising from PS oxidation and bromination by Br were observed for the first time. This work provides a better understanding of the reactivity and fate of BFRs in polymers allowing for a better assessment of their environmental impacts.
溴系阻燃剂（BFRs）作为添加剂广泛应用于塑料、纺织品和电子材料中。在这里，我们研究了四种 BFRs 的光降解，包括十溴联苯醚（BDE-209）、四溴双酚 A（TBBPA）、四溴双酚 A-双（2,3-二溴丙基醚）（TBBPA-DBPE）和四溴双酚 A 双（烯丙基）醚（TBBPA-BAE）。实验在聚苯乙烯（PS）薄膜中进行，采用单色和多色辐照。为了比较，还在溶剂（四氢呋喃：THF）中进行了辐照。通过体相和表面红外（IR）测量、提取和 HPLC-UV 监测 BFR 降解。使用 HPLC-高分辨率电喷雾电离质谱（HPLC-ESI-Orbitrap-MS）对光产物进行了表征。在 290nm 处，四种 BFRs 在 THF 中均发生光化学转化，量子产率（Φ）范围从 TBBPA 的 0.05 到 BDE-209 的 0.27，表明 BFRs 中 Br 原子数目的增加会提高光反应性。另一方面，当 BFRs 嵌入 PS 薄膜中时，Φ 值没有明显差异（Φ：0.82-0.89）。在 PS 中更高的光反应性似乎与 PS 的快速氧化有关，这可以通过红外（IR）分析和薄膜变黄来揭示。有趣的是，变黄发生得越快，由于光屏蔽效应，BFR 降解受到的抑制就越快。确定了 TBBPA 和 TBBPA-DBPE 的几种主要光产物。首次观察到可能由 PS 氧化和 Br 溴化引起的额外光产物。这项工作更好地了解了 BFRs 在聚合物中的反应性和归宿，从而能够更好地评估它们对环境的影响。
