The role of intermolecular interactions on melt memory and thermal fractionation of semicrystalline polymers

Leire Sangroniz, Yoon Jung Jang, Marc A. Hillmyer, Alejandro J. Müller

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Abstract

The origin of melt memory effects associated with semicrystalline polymers and the physical parameters involved in this process have been widely studied in the literature. However, a comprehensive understanding of the role of intermolecular interactions on melt memory is still being developed. For this purpose, we have considered aliphatic polyesters and we have incorporated amide and additional ester groups. Inserting these additional functional groups, the strength of the intermolecular interactions increases widening the melt memory effect. Not only the presence of the functional groups but also the position of these groups in the repeating unit plays a role in the melt memory effect as it impacts the strength of the intermolecular interactions in the crystals. The study of the effect of intermolecular interactions has been extended to successive self-nucleation and annealing thermal fractionation experiments to explore for the first time the role of intermolecular forces on the fractionation capacity of linear polymers. We demonstrated that intermolecular interactions act as intrinsic defects interrupting the crystallizable chain length, thus facilitating thermal fractionation. Overall, this work sheds light on the role of intermolecular interactions on the crystallization behavior of a series of aliphatic polyesters.

Original languageEnglish (US)
Article number144902
JournalJournal of Chemical Physics
Volume156
Issue number14
DOIs
StatePublished - Apr 14 2022

Bibliographical note

Funding Information:
The authors acknowledge funding from the NSF Center for Sustainable Polymers at the University of Minnesota, which is a National Science Foundation-supported Center for Chemical Innovation (Grant No. CHE-1901635). The authors also acknowledge the funding from the Basque Government (Grant No. IT1309-19) and MICINN (Project No. PID2020-113045GB-C21). L.S. acknowledges the postdoctoral fellowship from the Basque Government.

Publisher Copyright:
© 2022 Author(s).

PubMed: MeSH publication types

  • Journal Article

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