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聚碳酸酯基四溴双酚 A 在氧化铜存在下热解过程中含溴产物的抑制。

Mitigation of bromine-containing products during pyrolysis of polycarbonate-based tetrabromobisphenol A in the presence of copper(I) oxide.

机构信息

Department of Environmental Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Katsura C-1-3, 615-8540 Kyoto, Japan; Institute of Environmental Engineering of the Polish Academy of Sciences, M. Sklodowska-Curie 34, 41-819 Zabrze, Poland.

Graduate School of Environmental Studies, Tohoku University, 6-6-07 Aoba, Aramaki-Aza, Aoba-ku, Sendai 980-8579, Japan.

出版信息

J Hazard Mater. 2021 May 5;409:124972. doi: 10.1016/j.jhazmat.2020.124972. Epub 2020 Dec 25.

Abstract

Polycarbonate (PC) is an engineering thermoplastic that is widely used in electrical and electronic equipment. This plastic often contains tetrabromobisphenol A (TBBA), the most common brominated flame retardant. Thermal degradation of the PC-TBBA leads to generation of numerous bromo-organic products in the pyrolytic oil, hindering its appropriate utilization, as well as corrosive hydrogen bromide gas. The purpose of this study was to experimentally investigate and compare the pyrolysis products of PC-TBBA and PC-TBBA + CuO at various temperatures, with an emphasis on the yield and distribution of brominated compounds. In pyrolysis of PC-TBBA + CuO, at the maximum degradation temperature (600 °C), as much as 86% of total Br was trapped in the residue, while 3% and 11% were distributed in the condensate and gas fractions, respectively. In contrast, the distribution of Br from non-catalytic pyrolysis of PC-TBBA (600 °C) was 0.5% residue, 40% condensate, and 60% gas. The results of this study revealed that in the presence of CuO, organo-bromine products were most likely involved in Ullman-type coupling reactions, leading to early cross-linking of the polymer network that efficiently hinders their vaporization. HBr in the gas fraction was suppressed due to effective fixation of bromine in residue in the form of CuBr.

摘要

聚碳酸酯(PC)是一种工程热塑性塑料,广泛应用于电气和电子设备中。这种塑料通常含有四溴双酚 A(TBBA),这是最常见的溴化阻燃剂。PC-TBBA 的热降解会导致热解油中产生许多溴有机产物,阻碍了其适当的利用,并产生腐蚀性的溴化氢气体。本研究的目的是实验研究和比较 PC-TBBA 和 PC-TBBA+CuO 在不同温度下的热解产物,重点是溴化化合物的产率和分布。在 PC-TBBA+CuO 的热解中,在最大降解温度(600°C)下,多达 86%的总 Br 被截留在残渣中,而 3%和 11%分别分布在冷凝物和气体馏分中。相比之下,非催化热解 PC-TBBA(600°C)的 Br 分布为 0.5%的残渣、40%的冷凝物和 60%的气体。本研究的结果表明,在 CuO 的存在下,有机溴产物很可能参与 Ullman 型偶联反应,导致聚合物网络的早期交联,有效地阻止了它们的蒸发。由于溴以 CuBr 的形式有效地固定在残渣中,气体馏分中的 HBr 被抑制。

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