Trace analysis of airborne aromatic isocyanates and related aminoisocyanates and diamines using high-performance liquid chromatography with ultraviolet and electrochemical detection

A high-performance liquid chromatographic method was developed for trace analysis of complex air mixtures containing 2,6- and 2,4-toluenediisocyanates and related aminoisocyanates and diamines. The accuracy was tested at isocyanate concentrations of 2-1000 microg/m3 in air. The method is based on derivatization in the sampling step of isocyanate functions to corresponding urethane groups, with alkaline ethanol as the sampling and reacting medium. The derivatives formed, toluenediurethanes and tolueneaminourethanes, and unreacted diamines were detected by UV or electrochemically, the electrochemical detection being one order of magnitude more sensitive. Using an enrichment column, detection limits of ca. 0.05 pg/microl were obtained with electrochemical detection at a potential of 950 mV, which corresponds to air concentrations of 0.1 microg/m3 with 5 min sampling time at a rate of 11/min. The precision in the measurements were ca. 4% at concentrations of 6 microg/m3. A field measurement was performed concerning flame lamination of toluenediisocyanate-based polyurethane and cloth. Isocyanates, aminoisocyanates and diamines were found at air concentrations of 1-100 microg/m3.