Inter and intra molecular dynamics in poly(trimethylene 2,5-furanoate) as revealed by infrared and Broadband Dielectric Spectroscopies

Gálvez, Óscar; Toledano, Oscar; Hermoso, Francisco Javier; Linares, A.; Sanz, Mikel; Rebollar, Esther; Nogales, Aurora; García-Gutiérrez, Mari Cruz; Santoro, Gonzalo; Irska, Izabela; Paszkiewicz, Sandra; Szymczyk, Anna; Ezquerra, Tiberio A.

doi:10.1016/j.polymer.2023.125699

Cited by 9 publications

(24 citation statements)

References 54 publications

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“…Figure shows the FTIR absorption spectra of PTF at 25 °C. The FTIR spectrum of the PTF corresponds to a fully amorphous sample, as proven by GIWAXS and in accordance with previous studies. ,, …”

Section: Results and Discussionsupporting

confidence: 90%

“…The FTIR spectrum of the PTF corresponds to a fully amorphous sample, as proven by GIWAXS and in accordance with previous studies. 7,9,40 The main normal modes associated with the absorption bands of amorphous PTF have been indicated in Figure 4. Table 1 collects all of the different bands and the assignment of the vibration normal modes proposed.…”

Section: Ftir Of Ptfmentioning

confidence: 99%

“…A 0.25 mL drop of the polymer solution in trifluoroacetic acid (Sigma-Aldrich, reagent grade ≥98%) with a concentration of 50 g/L was deposited on a circular silicon substrate. The spin-coating conditions were 2400 rpm for 120 s. Under these conditions, the spin-coated films of PTF are amorphous according to FTIR and GIWAXS measurements . The film thickness was selected in order to have an optimal FTIR absorbance without a significant band saturation effect in the whole spectral range.…”

Section: Experimental Sectionmentioning

confidence: 99%

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Study of the Crystal Structure and Hydrogen Bonding during Cold Crystallization of Poly(trimethylene 2,5-furandicarboxylate)

Toledano,

Gálvez,

Sanz

et al. 2024

Macromolecules

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Here, we present a detailed description of the in situ isothermal crystallization of poly(trimethylene 2,5-furandicarboxylate)(PTF) as revealed by realtime Fourier transform infrared spectroscopy (FTIR) and grazing incidence wideangle X-ray scattering (GIWAXS). From FTIR experiments, the evolution of hydrogen bonding with crystallization time can be monitored in real time, while from GIWAXS, crystal formation can be followed. Density functional theory (DFT) calculations have been used to simulate FTIR spectra for different theoretical structures, enabling a precise band assignment. In addition, based on DFT ab initio calculations, the influence of hydrogen bonding on the evolution with crystallization time can be understood. Moreover, from DFT calculations and comparison with both FTIR and GIWAXS experiments, a crystalline structure of poly(trimethylene 2,5furandicarboxylate) is proposed. Our results demonstrate that hydrogen bonding is present in both the crystalline and the amorphous phases and its rearrangement can be considered as a significant driving force for crystallization of poly(alkylene 2,5-furanoate)s.

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Section: Results and Discussionsupporting

confidence: 90%

Section: Ftir Of Ptfmentioning

confidence: 99%

Section: Experimental Sectionmentioning

confidence: 99%

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Study of the Crystal Structure and Hydrogen Bonding during Cold Crystallization of Poly(trimethylene 2,5-furandicarboxylate)

Toledano,

Gálvez,

Sanz

et al. 2024

Macromolecules

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“…In other words, the CO stretching modes of amorphous PEF supports again the presence of the isomerism of FDCA moieties even at room condition . Very recently, Galvez et al also reported the extremely similar CO absorptions of 1744 and 1721 cm –1 in the amorphous poly(trimethylene 2,5-furanoate), and ascribed the two bands to syn and anti conformations of FDCA moieties respectively based on their calculations . If we ignore the temperature effect of vibration frequency, the crystalline CO band of PBF at 1731 cm –1 also can be well fitted, as illustrated in Figure D.…”

Section: Resultsmentioning

confidence: 57%

“…14 Very recently, Galvez et al also reported the extremely similar C�O absorptions of 1744 and 1721 cm −1 in the amorphous poly(trimethylene 2,5-furanoate), and ascribed the two bands to syn and anti conformations of FDCA moieties respectively based on their calculations. 58 If we ignore the temperature effect of vibration frequency, the crystalline C�O band of PBF at 1731 cm −1 also can be well fitted, as illustrated in Figure 3D. The perfect overlaps of the experimental spectra and the fitted curves ensure the reliability of above assignments.…”

Section: Ftir Evidences Of Intermolecular �C−h•••o�c Hydrogen Bonding...mentioning

confidence: 74%

Intermolecular ═C–H···O═C Hydrogen Bonding and Conformational Preference in Crystalline Poly(butylene 2,5-furandicarboxylate)

Shao

Long

et al. 2023

Macromolecules

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Besides maximizing packing efficiency, molecular interactions also play an indispensable role upon conformational ordering for crystallization of long-chain polymers. Herein, structural evolution upon heating of biobased poly(butylene 2,5-furandicarboxylate) (PBF) is followed by temperature-dependent infrared (IR) spectroscopy and wide-angle X-ray diffraction (WAXD) to elucidate the molecular interactions and conformational preference in its crystalline state. By estimating the group distances according to atomic coordinates of its crystal structure, the stronger intermolecular interaction than the van der Waals force is speculated to exist in crystalline PBF, which is fully confirmed by the changes of IR absorptions associated with C–H and CO groups upon heating as an abnormal C–H···OC hydrogen bonding. The combination of temperature-dependent C–H band position and crystal lattice expanding supports a good thermostability of this interaction up to melting, fully defining its nature as strong hydrogen bonding rather than the generally reported weak H···OC bonding in biodegradable polyesters. By further analyzing the confirmational ordering in its crystalline state, it is believed that such intermolecular C–H···OC hydrogen bonding stabilizes the energetically inaccessible syn–syn conformer of 2,5-furandicarboxylic moieties for PBF crystallization.

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Superior barrier performance, mechanical properties and compostability in relation to supramolecular structure of renewable based poly(trimethylene furanoate) modified with suberic acid

Zubkiewicz,

Szymczyk,

Dryzek

et al. 2024

European Polymer Journal

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Inter and intra molecular dynamics in poly(trimethylene 2,5-furanoate) as revealed by infrared and Broadband Dielectric Spectroscopies

Cited by 9 publications

References 54 publications

Study of the Crystal Structure and Hydrogen Bonding during Cold Crystallization of Poly(trimethylene 2,5-furandicarboxylate)

Study of the Crystal Structure and Hydrogen Bonding during Cold Crystallization of Poly(trimethylene 2,5-furandicarboxylate)

Intermolecular ═C–H···O═C Hydrogen Bonding and Conformational Preference in Crystalline Poly(butylene 2,5-furandicarboxylate)

Superior barrier performance, mechanical properties and compostability in relation to supramolecular structure of renewable based poly(trimethylene furanoate) modified with suberic acid

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