Extractable organic compounds in polyurethane foam with special reference to aromatic amines and derivatives thereof

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 (mu)g 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 4,4ʹ-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 (mu)g g^-1 foam, respectively. When flexible foam was heated, considerable higher concentrations of TDA were observed.