Thermochimica Acta 421 (2004) 95–103 Evaporation and thermal degradation of tetrabromobisphenol A above the melting point Katia Marsanich a , Severino Zanelli a , Federica Barontini b , Valerio Cozzani c,∗ a Dipartimento di Ingegneria Chimica, Chimica Industriale e Scienza dei Materiali, Università degli Studi di Pisa, via Diotisalvi n.2, 56126 Pisa, Italy b Gruppo Nazionale per la Difesa dai Rischi Chimico-Industriali ed Ecologici, Consiglio Nazionale delle Ricerche, via Diotisalvi n.2, 56126 Pisa, Italy c Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Università degli Studi di Bologna, viale Risorgimento n.2, 40136 Bologna, Italy Received 29 January 2004; received in revised form 24 March 2004; accepted 27 March 2004 Available online 20 May 2004 Abstract The volatility and the thermal degradation process of tetrabromobisphenol A (TBBA) were investigated. The quantitative assessment of the thermal degradation process and of the evaporation rate of TBBA required the use of an integrated approach, based on different calorimetric and analytical techniques. TBBA decomposition was carried out at temperatures between 180 and 270 ◦ C, using thermogravimetric (TG) devices and a laboratory-scale batch reactor. The identification and quantification of decomposition products was based on GC and GC/MS techniques. The apparent kinetic parameters for TBBA decomposition were obtained, and a simplified method was used for a rough estimate of the vapor pressure from TG data. Thermal degradation of TBBA, although present even at temperatures as low as 185 ◦ C, becomes relevant only above 230 ◦ C. A preliminary evaluation of the Antoine correlation parameters for TBBA showed that the vapor pressure of this compound is comprised between 0.1 and 5 Pa at temperatures between 180 and 270 ◦ C. The results obtained confirmed that TBBA processing at temperatures above the melting point (180 ◦ C) may cause the release of TBBA in the environment due to evaporation phenomena. © 2004 Elsevier B.V. All rights reserved. Keywords: Tetrabromobisphenol A; Thermal stability; Thermal degradation; Volatile emission; Evaporation 1. Introduction Tetrabromobisphenol A (TBBA) is the most important brominated flame retardant (BFR), representing about 50% of BFR total production. About 120 000 metric tons of TBBA were produced in 1999 [1]. The main use of TBBA is for the production of brominated epoxy resins for printed circuit boards, containing up to 20–25 wt.% bromine. How- ever, TBBA is also used as an additive flame retardant, mainly in the production of acrylonitrile–butadiene–styrene copolymers. In recent years, a growing concern was raised on envi- ronmental and toxicity issues related to the use of TBBA in electronic products that have a widespread diffusion. Several studies examined TBBA exposure in computer workers [2–5], and TBBA toxicity was the object of many ∗ Corresponding author. Tel.: +39-0512093141; fax: +39-051581200. E-mail address: valerio.cozzani@mail.ing.unibo.it (V. Cozzani). investigations [6–8]. The current state of knowledge about environmental sources, behavior and toxicity of BFR was recently reviewed [9,10]. The present regulatory tendency to improve the recycling of polymer material waste from electrical and electronic equipment in which BFR and in particular TBBA are largely present, requires new data on thermal stability and reactions of these flame retardants. The possible formation of hazardous products during ther- mal degradation processes of materials containing TBBA was examined by several authors [11–27]. However, while a number of studies were focused on the selective analysis of polybrominated dibenzo-p-dioxins and dibenzofurans formed in TBBA thermal degradation, limited data are present on TBBA thermal stability and thermal decomposi- tion products. Only few investigations were concerned with the analysis of TBBA thermal degradation process [20–22]. Further complementary data are available for brominated epoxy resins and printed circuit boards [23–27]. Although the presence of evaporation phenomena was observed by 0040-6031/$ – see front matter © 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.tca.2004.03.013