Quantitative pyrolysis - gas chromatography - mass spectrometry to study polymer dissolution and solubility

In recent years pyrolysis - gas chromatography - mass spectrometry (Py-GC-MS) has emerged as a powerful quantitative method to study polymeric samples. Improvement in the instrumentation, especially the introduction of programmed-temperature-vaporization (PTV) injectors for Py-GC, have made it possible to inject liquid samples (such as polymer solutions) automatically. Py-(PTV)GC-MS is a remarkably precise, robust and reliable method. Large volumes of sample can be injected, in a variety of different solvents. This includes water, which is a notoriously difficult solvent in combination with GC. Thermochemolysis has been introduced to deal with polymers that yield polar products during pyrolysis. Very low detection limits can be achieved, allowing the detection of dissolved polymers in the ppb (ng mL-1) range or even lower. Py-GC-MS additionally can yield information on polymer composition (e.g. in case of copolymers). In combination with size-exclusion chromatography, Py-GC-MS allows us to estimate the molecular-weight distributions of minute amounts of a dissolved polymer and variations therein as a function of time. These advancements have been explored in this thesis to study the dissolution and solubility of synthetic polymers.