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Abstract Chemical reactions between carbon dioxide (CO) and amine have been extensively characterized, however, their influence on the dynamics of polyamines remains largely unexplored. In this work, we compare the dynamics of polyethylenimine (PEI) before and after CO absorption through broadband dielectric spectroscopy (BDS). The molecular processes of bulk PEI are very different from those of thin film PEI, highlighting an interesting interface and nano‐confinement effect. Detailed analyses show CO absorption slows down the PEI dynamics, which is consistent with an elevated glass transition temperature of PEI upon CO absorption from differential scanning calorimetry measurements. Furtherin situkinetic measurements demonstrate nonmonotonic changes in relaxation times or dielectric amplitudes of some relaxation processes during CO sorption or desorption, suggesting an intriguing interplay between CO chemisorption and the dynamics of PEI. These results demonstrate that BDS is a powerful platform to resolve the temporal dynamics changes of polyamines for CO capture. 

Recent findings that the association bond lifetimes τ α* in associating polymers diverge from their supramolecular network relaxation times τ c challenge past theories. The bond lifetime renormalization proposed by Rubinstein and coworkers [Stukalin et al. , Macromolecules , 2013, 46 , 7525] provides a promising explanation. To examine systematically its applicability, we employ shear rheology and dielectric spectroscopy to study telechelic associating polymers with different main chain (polypropylene glycol and polydimethylsiloxane), molecular weight (below entanglement molecular weight) and end groups (amide, and carboxylic acid) which form dimeric associations by hydrogen bonding. The separation between τ c (probed by rheology) and τ α* (probed by dielectric spectroscopy) strongly increases with chain length as qualitatively predicted by the model. However, to describe the increase quantitatively, a transition from Rouse to reptation dynamics must be assumed. This suggests that dynamics of super-chains must be considered to properly describe the transient network.