Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5-furanoate)

Abstract

We report on the molecular origin of poly(pentamethylene 2,5-furanoate) particular physical properties. From the structural point of view we found this polymer can develop crystallinity when stored at room conditions for months. On the other hand, we used broadband dielectric spectroscopy (BDS) measurements, to analyze in very detail the local and segmental molecular dynamics of the material subjected to several thermal treatments. In this way we evidenced that the molecular dynamics are sensitive to thermal history over a broad temperature range. This behavior has been attributed to possible inter-chain interactions detected via infrared spectroscopy and rheology measurements in the non-crystallized polymer.

Sustainable textile fibers of bioderived polylactide/poly(pentamethylene 2,5‐furanoate) blends

“…Figure 6a reports the thermograms referring to the first heating scan, and it is possible to notice that the as received PPeF utilized in this work is fully amorphous, showing a T g at 17.2 C, which is a temperature close to that found in literature for this material. 43 Being amorphous is a characteristic of the polyesters with a C-odd-numbered glycolic subunit, like PPeF, while those with a C-even-numbered glycolic subunit, such as PBF, POF, PDeF, tend to develop a crystalline structure. 44,51,77 Furthermore, PLA exhibits a T g at 54.1 C, a cold crystallization peak at 96.5 C, and an endothermic melting peak at 166.2 C. Interestingly, both the T g and the T m of PLA are unaltered by the addition of PPeF, and this further confirms that PLA and PPeF are immiscible.…”

“…As reported by Papageorgiou et al, 30 also semicrystalline PPeF could be synthesized, depending on the molecular weight and the processing conditions. Martinez‐Tong et al 43 performed a comprehensive study on the thermal properties of PPeF undergoing different thermal histories. From the DSC analysis, they observed that PPeF was amorphous, but if the PPeF sample was kept for 18 months at room temperature, it reported multiple melting phenomena, which is typical of semicrystalline polymers 43 .…”

“…From the DSC analysis, they observed that PPeF was amorphous, but if the PPeF sample was kept for 18 months at room temperature, it reported multiple melting phenomena, which is typical of semicrystalline polymers. 43 In a parallel work of our group, thin films made of PLA/PPeF have been prepared through solvent casting and the thermomechanical properties of the obtained materials were strictly correlated to their microstructural features. The drop of stiffness and failure properties upon PPeF introduction was largely compensated by a strong enhancement of strain at break, especially with a furanoate amount of 30 wt%.…”

“…Martinez‐Tong et al 43 performed a comprehensive study on the thermal properties of PPeF undergoing different thermal histories. From the DSC analysis, they observed that PPeF was amorphous, but if the PPeF sample was kept for 18 months at room temperature, it reported multiple melting phenomena, which is typical of semicrystalline polymers 43 . In a parallel work of our group, thin films made of PLA/PPeF have been prepared through solvent casting and the thermomechanical properties of the obtained materials were strictly correlated to their microstructural features.…”

“…37 On the other hand, it is characterized by a brittle behavior at room temperature, and this feature (together with the elevated price of FDCA) limited its use in different industrial applications. Besides PEF several homopolyesters, derived from the polymerization reaction between FDCA and aliphatic diols with a higher number of carbon atoms, have been recently synthesized, like poly(propylene 2,5-furandicarboxylate) (PPF), 38 poly(butylene 2,5-furandicarboxylate) (PBF), 39,40 poly(pentamethylene 2,5-furanoate) (PPeF), [41][42][43][44] poly (hexamethylene 2,5-furandicarboxylate) (PHF), 42,45 poly(octylene 2,5-furandicarboxylate) (POF), 46 poly (decylene 2,5-furandicarboxylate) (PDeF) 47,48 and poly(dodecylene 2,5-furandicarboxylate) (PDoF). 49 The direct consequence of the increase in the number of carbon atoms of the diol is the decrease of the thermo-mechanical properties of the resulting furan-based polyester furanoate, in terms of elastic modulus (E), glass transition temperature (T g ), and melting temperature (T m ).…”