Migration from can coatings: Part 2. Identification and quantification of migrating cyclic oligoesters below 1000 Da

Abstract

Metal cans for food use can be coated with lacquers based on polyester resins. Recent research has focussed on the identification and quantification of migrants released by coatings that are potentially absorbable (below 1000 Da). The presented method describes a procedure that was optimized to hydrolyse the polyester migrants into their monomers, polyvalent acids and polyols. The polyols were identified by gas chromatography with flame ionization detection GC-FID and the acids by high-performance liquid chromatography (HPLC) coupled with an ultraviolet and an electrospray ionization-mass selective detector (HPLC-ESI-MSD/UVD), respectively. With the knowledge of the polyester monomers, it was possible — at least tentatively — to identify the main components in the migrate as cyclic oligoesters by HPLC-ESI-MSD/UVD. A cyclic oligomer, CYCLO [3IPA (isophthalic acid) 3EG (ethylene glycol)] was synthesized and characterized by infrared, nuclear magnetic resonance and mass spectrometry as well as by elementary analysis for further confirmation. To determine the amount of migrating cyclic oligoesters, the response of the migrating substances was compared using different detectors, UVD, MSD and evaporative light scattering detector (ELSD). The response of the ELSD was dependent on the molecular weight of the analytes that reduced the accuracy of this detection type. The wavelength with the same absorption coefficient for IPA and terephthalic acid (TPA) was obtained at 232 nm. The UV_232nm response of an oligoester is proportional to the number of its IPA/TPA moieties, which was verified for several TPA/IPA esters. The amount of the migrating oligoesters was determined using an UV_232nm calibration of a commercially available TPA ester and the number of IPA/TPA moieties molecules gained from the ESI-MSD spectra. According to this method, the amount of migrating oligoesters below 1000 Da in the 95% ethanol migrate varied from 0.1 to 0.6 mg dm⁻² (0.6–3.6 mg kg⁻¹ food) in the examined coatings. The determined amounts account for about 50% of the total migrate below 1000 Da.

Keywords:

• food packaging
• can coatings
• migration
• cyclic oligoesters
• polyester hydrolysis
• HPLC-ESI-MSD/UVD
• HPLC-ELSD
• GC-FID

Acknowledgements

The study was supported financially by Valspar Corporation. The authors thank Peter Oldring for coordinating the migration project. NMR analyses were carried out by the Department of Organic Chemistry and Elementary Analysis by the central element analysis of the University of Hamburg.