Effect of intermolecular interactions on the glass transition temperature of chemically modified alternating polyketones

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datacite.alternateIdentifier.citationMATERIALS TODAY CHEMISTRY,Vol.34,2023
datacite.alternateIdentifier.doi10.1016/j.mtchem.2023.101771
datacite.creatorCortes, Pablo Gonzalez
datacite.creatorAraya Hermosilla, Rodrigo
datacite.creatorWrighton Araneda, Kerry
datacite.creatorCortes Arriagada, Diego
datacite.creatorPicchioni, Francesco
datacite.creatorYan, Feng
datacite.creatorRudolf, Petra
datacite.creatorBose, Ranjita K.
datacite.creatorQuero, Franck
datacite.date2023
datacite.subject.englishPolyketone
datacite.subject.englishPaal-knorr reaction
datacite.subject.englishSupramolecular networks
datacite.subject.englishPolymer chemistry
datacite.subject.englishHydrogen bonding
datacite.subject.englishTuneable phase transition
datacite.subject.englishALMO-EDA
datacite.titleEffect of intermolecular interactions on the glass transition temperature of chemically modified alternating polyketones
dc.date.accessioned2024-05-27T18:27:51Z
dc.date.available2024-05-27T18:27:51Z
dc.description.abstractThermal properties of polymers depend on the chemical structure of the polymer chain and intermolecular forces arising from hydrogen bonding and pi-pi stacking. Here we analyzed the effect of increasing the amount of supramolecular interactions on the glass transition temperature of polyketones by chemically modifying the same polymer backbone with five amine derivatives, namely (1-(3-aminopropyl)-imidazole, 4-(aminomethyl) benzoic acid, 6-aminohexanoic acid, benzylamine or hexylamine, at various molar concentrations. The grafting was performed via the Paal-Knorr reaction and the interactions between the pyrrole backbone and different grafted functional groups were elucidated by proton nuclear magnetic resonance, Fourier transform infrared and X-ray photoelectron spectroscopy as well as differential scanning calorimetry and computational modeling. The modification of polyketone with 4-(aminomethyl) benzoic acid and 6-aminohexanoic acid, allowed for new possibilities of hydrogen bonding and led to a significant increase in the glass transition temperature as compared to the neat polymer and pyrrole-containing polymers that did not bear reactive side groups. In contrast, modification with the imidazole derivative was found to introduce new and more robust CHMIDLINE HORIZONTAL ELLIPSIS pi interactions between imidazole groups and the pi-system of the pyrrole backbone chain, based on electrostatic effects. Both types of supramolecular interactions affect the mobility of the backbone chains and this systematic study demonstrates how the combined effect of pi-pi stacking and hydrogen bonding to carboxylate moieties can be used to tune the molecular mobility and phase transition temperature of these chemically modified polyketones.
dc.identifier.urihttps://repositoriodigital.uct.cl/handle/10925/5870
dc.language.isoen
dc.publisherELSEVIER SCI LTD
dc.sourceMATERIALS TODAY CHEMISTRY
oaire.resourceTypeArticle
uct.indizacionSCI
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