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Title: Correlation between locally ordered (hydrogen-bonded) nanodomains and puzzling dynamics of polymethysiloxane derivative
Authors: Tarnacka, Magdalena
Jurkiewicz, Karolina
Hachuła, Barbara
Wojnarowska, Żaneta
Wrzalik, Roman
Talik, Agnieszka
Maksym, Paulina
Kamiński, Kamil
Paluch, Marian
Keywords: Fourier transform infrared spectroscopy; Physical and chemical processes; Insulators; Silicones; Polymers
Issue Date: 2020
Citation: "Macromolecules" (2020), iss. 22, s. 10225-10233
Abstract: We examined the behavior of poly(mercaptopropyl)methylsiloxane (PMMS), characterized by a polymer chain backbone of alternate silicon and oxygen atoms substituted by a polar pendant group able to form hydrogen bonds (−SH moiety), by means of infrared (FTIR) and dielectric (BDS) spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and rheology. We observed that the examined PMMS forms relatively efficient hydrogen bonds leading to the association of chains in the form of ordered lamellar-like hydrogen-bonded nanodomains. Moreover, the recorded mechanical and dielectric spectra revealed the presence of two relaxation processes. A direct comparison of collected data and relaxation times extracted from two experimental techniques, BDS and rheology, indicates that they monitor different types of the mobility of PMMS macromolecules. Our mechanical measurements revealed the presence of Rouse modes connected to the chain dynamics (slow process) and segmental relaxation (a faster process), whereas in the dielectric loss spectra we observed two relaxation processes related most likely to either the association−dissociation phenomenon within lamellar-like self-assemblies or the sub-Rouse mode (α′-slower process) and segmental (α-faster process) dynamics. Data presented herein allow a better understanding of the peculiar dynamical properties of polysiloxanes and associating polymers having strongly polar pendant moieties.
DOI: 10.1021/acs.macromol.0c01289
ISSN: 1520-5835
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