Retention indices as identification tool in pyrolysis-capillary gas chromatography

Pyrolysis-capillary gas chromatography (Py-cGC) represents important method to identify the analytes in the mixture after thermal degradation. This combines high effective analyte separation on-line coupled with thermal degradation process that depends on analyte structure. System of retention indices has been used for identification of the analytes after on-line pyrolysis and chromatographic separation. The pyrolysate composition has been studied during thermal degradation of polymethylmethacrylate (PMMA) at different pyrolysis temperatures and chromatographic column conditions. Homologues series of n-alkanes have been used for calculation of pyrolysate Kováts retention indices (I) and compared with mass spectrometric (MS) data of pyrolysate model mixture. To identify PMMA thermal degradation products the high density polyethylene (HDPE) as additive standard producing triplets of the olefin homologous series during co-pyrolysis has been used. These homologous series enable to calculate programmed temperature retention indices (ITPGC) to identify the analytes present in the pyrolysate. Calculated I values were compared with published I values databases to identify analytes yielded at different pyrolysis temperatures.