Carbon Dioxide Sorption and Transport in Amorphous Poly(ethylene furanoate)

Abstract

Transport properties of carbon dioxide in amorphous poly(ethylene furanoate) (PEF) were investigated using complementary pressure-decay sorption and permeation techniques. Detailed measurements for PEF at 35 °C indicate a significant, surprisingly large reduction in carbon dioxide permeability of 19× at 1 atm compared to poly(ethylene terephthalate) (PET), despite both an increase in free volume and carbon dioxide solubility of 1.6× for PEF vs PET. The solubility increase for PEF, which originates from greater interaction between carbon dioxide and the polar furan moiety, is offset by a substantial reduction in diffusivity of 31× compared to PET. Such diffusion reduction for PEF, which is 3× greater than the 9.7× reduction in oxygen diffusivity compared to PET, is thought to originate from a hindrance of polymer ring-flipping motions compared to PET. A possible mechanism for the surprising barrier improvement for carbon dioxide in PEF vs PET is explained herein along with a detailed comparison to oxygen and water transport.

How high pressure CO2 impacts PLA film properties

“…. For PET Similar D sorp values were also observed in other studies [40][41][42]. The variability of first sorption was higher than the others cycles, and for desorption steps, the equilibrium was reached faster than for sorption.…”

Poly(butylene 2,5-furandicarboxylate-ε-caprolactone): A new bio-based elastomer with high strength and biodegradability

“…Chemical structure and the real composition of PBFCL were confirmed by 1 H NMR analysis, as seen in Figure 2. Peaks at 7.42 ppm (a), 4.58 ppm (b) and 2.08 ppm (g) should be attributed to furan nucleus and protons of BDO in BF segments, which is in accordance with spectrum of PBF [9]. Similarly, peaks at 4.28 ppm (e), 2.54 ppm (f), 1.80 ppm (h), and 1.52 ppm (i) are assigned to methylene protons of -CH 2 -O-, -OC-CH 2 -, and -(CH 2 ) 3 -in CL segments [24].…”

“…In a fast-speed scan mode as shown in Figure 3a, PBFCL-20, PBFCL-30 and PBFCL-40 are all semi-crystalline polymers showing peaks at 2θ = 18.9, 22.4, and 25.0°. Those peaks are same in the same position as PBF homopolymer [9], confirming that PBFCL and PBF share the same crystalline structure formed by BF segments. Crystallinity of PBFCL decreases with increasing CL content owning to shorter sequence length of BF segments.…”

“…In the second stage, CL and Sb(Ac) 3 (0.1mol% CL) were added to the system to proceed ring-opening reaction initiated by the furanic α-ω hydroxyl oligomers at the temperature of 200°C and nitrogen atmosphere. The ring-opening reaction was proceeded for about 3 hours [9]. After that, the polycondensation reaction was conducted by increasing the temperature to 240 °C and reducing the pressure lower than 100 Pa. PBFCLs with different CL contents were obtained by controlling the weight ratio of ε-caprolactone to furanic α-ω hydroxyl oligomers in feed.…”

“…For example, poly(ethylene 2,5-furandicarboxylate) (PEF) [8] is being further developed and commercialized in beverage package for its excellent mechanical and barrier properties. PBF material has largely reduced carbon dioxide permeability (19×) and diffusivity (31×) compared to the respective properties of PET [9]. Other polyesters like poly(butylene 2,5-furandicarboxylate) (PBF) [10], poly(butylene adipate-co-butylene 2,5-furandicarboxylate) (PBAF) [11] and poly(butylene succinic-co-butylene 2,5-furandicarboxlylate) (PBSF) [12] with satisfying thermomechanical properties were also successfully prepared.…”