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.

Size-exclusion chromatography (SEC) and pyrolysis-gas chromatography (Py-GC) are commonly used to characterize copolymers. SEC is a powerful method to determine the molecular-weight distribution of polymers whereas Py-GC provides valuable information on their chemical composition. The combination of these two techniques could yield combined size and composition information for copolymers or polymer mixtures. A fully automated system was constructed to perform these two-dimensional (2D) characterizations...

Gas chromatography is an important analytical technique for qualitative and quantitative analysis in a wide range of application areas. It is fast, provides a high peak capacity, is sensitive and allows combination with a wide range of selective detection methods including mass spectrometry. However, the application area of GC is limited because the molecules to be analysed have to be thermally stable and sufficiently volatile. Numerous molecules do not meet these requirements and hence are not amenable to direct GC analysis. Recent research has resulted in better chromatographic columns and methods for sample preparation that enable a significant expansion of the molecular application range of GC. The strategies exploited include conversion of (macro)molecules into smaller species and approaches to reduce the polarity of molecules. In this review we identify four generic routes for extending the applicability of GC. These include high-temperature GC, derivatisation, pyrolysis and thermochemolysis. The principles, recent developments and future perspectives of these routes are discussed and examples of applications using the different options will be shown. Life sciences, metabonomics and profiling strategies for sample characterization are identified as important future drivers for the continued development of GC.

A recently developed hyphenated system for “organic” size-exclusion chromatography–pyrolysis-gas chromatography–mass spectrometry (SEC–Py-GC–MS) is adapted to allow the use of aqueous LC eluents as applied in the characterization of water-soluble polymers. The system uses syringe-based transfer of multiple LC-fractions to the GC instrument with solvent elimination and subsequent pyrolysis in a programmed temperature vaporization injector. The problems of the large-volume injections of aqueous, salt containing eluents into the Py-GC–MS are solved by using a ‘sintered-bed liner’ for elimination of the water at a high temperature, a volatile salt and the installation of a back-flush option. After optimization, the system was applied for the determination of the combined molecular weight–chemical composition of a polyethylene glycol–polypropylene glycol block copolymer. This analysis was done with the system in the aqueous SEC–Py-GC–MS mode. Also demonstrated is the automated at-line characterization of a random polystyrene–polymethylmethacrylate copolymer, now with the system in the gradient reversed-phase LC–Py-GC–MS mode. The methods proposed in the present work are very useful for the detailed characterization of water-soluble copolymers.