On-line size exclusion chromatography–pyrolysis-gas chromatography–mass spectrometry for copolymer characterization and additive analysis

On-line coupled size exclusion chromatography–pyrolysis gas chromatography mass spectrometry (SEC–Py-GC–MS) is studied as a novel tool for the characterization of complex polymer samples. An automated system for on-line SEC–Py-GC–MS allowing transfer of multiple fractions was developed based on stop-flow operation of the SEC dimension, syringe-based transfer of the SEC fraction to the GC instrument and solvent elimination with subsequent pyrolysis in a programmed temperature vaporization (PTV) injector. After optimization the system was applied to the characterization of a complex terpolymer composed of very similar monomers. The use of the system for combined pyrolysis and additive analyses in polycarbonate was also demonstrated. Results obtained with the new method indicate the interesting potentials of the method for detailed characterization of polymeric materials.