Influence of Carbon Dioxide on the Glass Transition of Styrenic and Vinyl Pyridine Polymers: Comparison of Calorimetric, Creep, and Rheological Experiments

The glass transition of amorphous polymers determines the mobility of polymer chains and the time scale of relaxation processes. The glass transition temperature is reduced by the presence of low molecular weight molecules, e.g., dissolved gases or organic solvents. The quantitative knowledge of reduction of the glass transition temperature caused by the addition of carbon dioxide in a polymer melt is highly relevant for foam extrusion. However, measurement of the reduction of glass transition temperature caused by gas loading has to be performed under elevated pressure which implies high experimental efforts. In this work, we discuss and compare three methods for determination of the influence of carbon dioxide on thermal properties of amorphous polymers, i.e., calorimetric measurements, creep tests, and rheological experiments. The advantages and disadvantages of these methods are elucidated. Furthermore, the influence of molecular structure of the styrenic and vinylpyridine polymers on the glass transition temperature is discussed. Polystyrene generally shows the highest reduction of glass transition temperature. Poly(2-vinylpyridine) and poly(4-vinylpyridine) show a slightly less pronounced behaviour in comparison to polystyrene because of the lower polarity of polystyrene. Poly(α-methyl styrene) is associated with a different dependence of glass transition temperature on gas loading in calorimetric and rheological experiments.