Synthesis of poly(ethylene furandicarboxylate) polyester using monomers derived from renewable resources: thermal behavior comparison with PET and PEN

Abstract

Poly(ethylene-2,5-furandicarboxylate) (PEF) is a new alipharomatic polyester that can be prepared from monomers derived from renewable resources like furfural and hydroxymethylfurfural. For this reason it has gained high interest recently. In the present work it was synthesized from the dimethylester of 2,5-furandicarboxylic acid and ethylene glycol by applying the two-stage melt polycondensation method. The thermal behavior of PEF was studied in comparison to its terephthalate and naphthalate homologues poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN), which were also synthesized following the same procedure. The equilibrium melting point of PEF was found to be 265 °C while the heat of fusion for the pure crystalline PEF was estimated to be about 137 J g(-1). The crystallization kinetics was analyzed using various models. PET showed faster crystallization rates than PEN and this in turn showed faster crystallization than PEF, under both isothermal and non-isothermal conditions. The spherulitic morphology of PEF during isothermal crystallization was investigated by polarized light microscopy (PLM). A large nucleation density and a small spherulite size were observed for PEF even at low supercoolings, in contrast to PET or PEN. Thermogravimetric analysis indicated that PEF is thermally stable up to 325 °C and the temperature for the maximum degradation rate was 438 °C. These values were a little lower than those for PET or PEN.

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

“…The ability of the copolymer to crystallize was drastically reduced with the addition of the comonomer and consequently increase of the elongation at break of the polymer [13]. These FDCA based polyesters have shown great prospective to replace their petroleumbased counterparts applied as plastic products [3,8]. However, the synthesis of FDCA based polyesters applied as thermoplastic elastomers has rarely been reported.…”

“…FDCA has been investigated intensively both in academia and industry because it is a perfect bio-based substitute to the petroleum-based terephthalate acid (TPA), which is a versatile monomer for polyester and poly amide [2,7]. 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].…”

5‐hydroxymethylfurfural conversion by fungal aryl‐alcohol oxidase and unspecific peroxygenase

“…These polymers are thought to be able to substitute for polyesters based on terephthalic acid, such as poly(ethylene-terephthalate), poly(propylene-terephthalate) or poly(butylene-terephthalate), which are biologically not degradable, and the precursors of which are fossil resources. Poly(ethylene-2,5-furandicarboxylate) exhibits good mechanical and barrier properties [5], and has the double advantage of being renewable and biodegradable. The oxidative pathway leading from HMF to FDCA takes place via 2,5-formylfurancarboxylic acid (FFCA) and its alternative precursors 2,5-diformylfuran (DFF) and 2,5-hydroxymethylfuran carboxylic acid (HMFCA) (Fig.…”

Biobased poly(ethylene furanoate-co-ethylene succinate) copolyesters: solid state structure, melting point depression and biodegradability

“…In terms of the thermodynamic parameters and the cocrystallization of synthesized from 2,5-FDCA and methanol as described in our previous work 56 . All other materials and solvents used were of analytical grade.…”