Biobased Poly(dodecylene Furanoate) with Inherent Advantages in Performance and Circularity

Abstract

Biobased polymers are gaining traction toward more sustainable flexible-film packaging, yet overcoming trade-offs between their performance properties and end-of-life (EoL) options still remains a challenge. Here, it is shown that biobased poly(dodecylene 2,5-furanoate) (PDDF), synthesized via both step-growth polycondensation and chain-growth ring-opening polymerization methods, exhibits advantages not only in gas barrier properties but also in EoL options due to its biodegradability and closed-loop chemical circularity. Specifically, PDDF displays significantly lower oxygen and carbon dioxide permeability than commercial poly(butylene adipate-co-terephthalate) (PBAT) and linear low-density polyethylene , alongside a markedly higher modulus (by ≈3 ×) and reduced water vapor transmission rate compared to PBAT. This superior performance is attributed to the inherently rigid, polar, H-bonding furan rings that enhance chain interaction, packing and crystallinity and thus reduce free volume impeding gas diffusion, while the long hydrophobic dodecylene segments inhibit water permeation. Furthermore, PDDF can be recycled back to its cyclic monomer by base-catalyzed depolymerization or diester and diol monomers by simple methanolysis. These superior barrier properties, coupled with biodegradation and closed-loop circularity, highlight the potential of the biobased PDDF as a more sustainable alternative for packaging.

Keywords: Poly(dodecylene 2,5‐furanoate) (PDDF); biobased polymer; biodegradation; chemical circularity; gas barrier.

Figure 1

Synthesis and chemical circularity of PDDF through dual circular paths via ring‐opening polymerization (ROP)/ring‐closing depolymerization (RCDP) and step‐growth polymerization (SGP)/methanolysis (MET) routes.

Figure 2

The molecular structure of the cyclic monomer DDFL obtained by single‐crystal X‐ray diffraction analysis and its expanded packing structure (a + 2, b + 1.5, c + 0). Carbon atoms in gray, oxygen atoms in red, and hydrogen atoms in black. The crystal data was deposited at the Cambridge Crystallographic Database Centre as CCDC‐2 359 161.

Figure 3

Thermal properties of PDDF, compared to commercial materials PBAT and LLDE. a) DSC first heating cycle. b) DSC first cooling cycle. c) DSC second heating cycle. d) TGA thermogram overlays. e) Derivative TGA (DTGA) thermogram overlays.

Figure 4

Isothermal crystallization kinetics. a) Isothermal crystallization for PDDF‐SGP. b) Avrami model results for PDDF‐SGP. c) Isothermal crystallization for PDDF‐ROP. d) Avrami model results for PDDF‐ROP.

Figure 5

Properties of PDDF crystallites, compared to PBAT and LLDPE. a) WAXS profiles for PDDF, PBAT, and LLDPE. b) SAXS profiles for PDDF, PBAT, and LLDPE. c) Orientation from SAXS for PDDF‐SGP and PDDF‐ROP in the thickness (0° and 180°) direction.

Figure 6

Mechanical, dynamic mechanical, and rheological properties of PDDF, compared to PBAT and LLDPE. a) Stress–strain curves for PDDF, PBAT, and LLDPE. b) DMA results for PDDF and PBAT. Storage modulus is represented as (‐ solid lines), and damping factor is represented as (‐ ‐ dashed lines). c) Complex viscosity curve of PDDF, PBAT, and LLDPE. d) Elongation viscosity curves for PDDF, PBAT, and LLDPE.

Figure 7

Gas barrier properties. Measurements of H₂O, O₂, and CO₂ permeability of PDDF, compared to commercial packaging/barrier materials PBAT and LLDPE.

Figure 8

Dual closed circular chemical loops established by catalyzed ring‐closing depolymerization (RCDP)/repolymerization (ROP) and methanolysis (MET)/repolymerization (SGP).

Figure 9

Chemical recyclability demonstration for PDDFL. ¹H NMR spectra (CDCl₃) of starting virgin monomer DDFL (top), recycled DDFL (second from top) monomer, and PDDF polymer by ROP (bottom).

Figure 10

PDDF biodegradability tests against reference materials (glucose and/or micro‐crystalline cellulose (MCC)). a) Freshwater biodegradation profile. b) Soil biodegradation profile. c) Compost biodegradation profile.