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We report dielectric and calorimetric studies on metathesis and addition-type polytricyclononenes, both based on the same monomer bearing three pendant OSiMe3 groups. For the addition-type polymer, dielectric spectroscopy reveals a β*-process related to the microporosity, whereas for its metathesis counterpart, the segmental dynamics manifests as an α-process related to a glass transition. Besides active dielectric processes, a significant conductivity contribution is detected for both samples which for the microporous additiontype polymer is three orders of magnitude greater than for the metathesis polymer. The broadband dielectric spectroscopy is complemented by detailed calorimetric investigations, comprising DSC, FSC, and TMDSC. The calorimetric methods detected the glass transition for the metathesis polymer in agreement with the observed dielectric α-process. Furthermore, the already reported gas transport properties for both polymers are compared, setting them in correlation with the observed molecular mobility and conductivity behavior. The discussed results reflect significant differences in molecular mobility of the two polymers affecting the appearance of microporosity which strongly determines the gas transport properties.
Polymers with intrinsic microporosity (PIMs) are of great interest in the field of gas separation membranes. Already the first synthesized PIM-1 shows extraordinary permeability and selectivity. Unfortunately, PIM-1 is susceptible to physical aging and thus gradually loses its outstanding properties. In this study a polyhedral oligomeric silsesquioxane with phenethyl substituents (PhenethylPOSS) was used as a nanofiller (0–40 wt%) in the PIM-1 matrix to potentially improve the gas transport properties and prevent physical aging. The molecular mobility of the solution-cast nanocomposite films was analyzed by Broadband Dielectric Spectroscopy (BDS). Furthermore, gas permeability was determined with the time lag method (0–20 bar upstream pressure) at 35 °C for N2, O2, CH4 and CO2.
Polymeric membranes represent a cost- and energy efficient solution for gas separation. Recently superglassy polymers with high free volume outperform many conventional dense polymers in terms of gas permeability and selectivity. However, such materials with a high fractional free volume (FFV) are prone to pronounced physical aging. The initial microporous structures approach a denser state via local chain rearrangements which results in a dramatic reduction in the gas permeability. For the first time, dielectric spectroscopy with state-of-the-art high-resolution analyzers was employed to investigate the molecular mobility and physical aging of two representative groups of superglassy polymers: PIMs (PIM-1 & PIM-EA-TB) and Si-containing polynobornenes (PTCNSi1 & PTCNSi2). The dielectric behavior of the solution-cast polymeric films was measured by isothermal frequency scans during the different heating cycles in a broad temperature range. Structural relaxation of the films was observed during the measurements. Multiple dielectric processes following Arrhenius behavior were observed for all the investigated polymers. Moreover, they all showed conductivity in the glassy state. The significant increase in the conductivity with increasing temperature especially for PIMs is explained in terms of the formation of local intermolecular agglomerated structures due to interaction of π-electrons in aromatic moieties of the polymer backbone.
Super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP) or polymers with intrinsic microporosity (PIMs) play an important role in the current development of membrane materials for gas separation because of their high permeability and selectivity. Unfortunately, such materials which have a high fractional free volume (FFV) are prone to pronounced physical aging. The initial microporous structures approach a more dense state via local chain rearrangements which results in a dramatic reduction in the gas permeability. For the first time, broadband dielectric spectroscopy was employed to investigate the molecular dynamics of two representative groups of super glassy polymers: PIMs (PIM-1 & PIM-EA-TB) and Si-containing polynobornenes (PTCNSi1 & PTCNSi2). The dielectric behavior of the solution-cast polymeric films was measured by isothermal frequency scans during the different heating cycles in a broad temperature range. Structural relaxation of the films was observed during the measurements. Molecular relaxation processes following Arrhenius behavior with unusually high activation energies were observed for all the investigated polymers. The PIMs showed furthermore a significant conductivity in the glassy state which is explained with the formation of local intermolecular agglomerated structures due to interaction of π-electrons in aromatic moieties of the polymer backbone.