Synthesis of bio‐based poly(ethylene 2,5‐furandicarboxylate) copolyesters: Higher glass transition temperature, better transparency, and good barrier properties

Abstract

The bio-based polyester, poly(ethylene 2,5-furandicarboxylate) (PEF), was modified by 2,2,4,4-tetramethyl-1,3cyclobutanediol (CBDO) via copolymerization and a series of copolyesters poly(ethylene-co-2,2,4,4-tetramethyl-1,3-cyclobutanediol 2,5-furandicarboxylate)s (PETFs) were prepared. After their chemical structures and sequence distribution were confirmed by nuclear magnetic resonance ( 1 H-NMR and 13 C-NMR), their thermal, mechanical, and gas barrier properties were investigated in detail. Results showed that when the content of CBDO unit in the copolyesters was increased up to 10 mol%, the completely amorphous copolyesters with good transparency could be obtained. In addition, with the increasing content of CBDO units in the copolyesters, the glass transition temperature was increased from 88.9 8C for PET to 94.3 8C for PETF-23 and the tensile modulus was increased from 3000 MPa for PEF to 3500 MPa for PETF-23. The barrier properties study demonstrated that although the introduction of CBDO units would increase the O 2 and CO 2 permeability of PEF slightly, PECF-10 still showed better or similar barrier properties compared with those of PEN and PEI. In one word, the modified PEF copolyesters exhibited better mechanical properties, higher glass transition temperature, good barrier properties, and better clarity. They have great potential to be the biobased alternative to the popular petroleum-based poly(ethylene terephthalate) (PET) when used as the beverage packaging materials.

One‐Step Lignocellulose Fractionation by using 2,5‐Furandicarboxylic Acid as a Biogenic and Recyclable Catalyst

“…FDCA has recently gained huge interest as a biomass‐derived molecule that exerts promising properties in different applications. For example, it has been proposed as an alternative polyester building block to replace terephthalic acid by forming the polyethylene furanoate (PEF) or as a precursor for fine chemicals . Interestingly, its use as a catalyst has hitherto been scarce, and only some recent examples illustrate its potential for dehydration or oxidoreduction processes .…”

Tuning the Properties of Furandicarboxylic Acid-Based Polyesters with Copolymerization: A Review

“…Titanium(IV) isopropoxide is regularly used, solely or in combination with TBT [ 28 , 29 , 60 , 68 , 77 , 93 , 97 , 100 ]. Zinc(II) acetate is also often used for the first step (Sb 2 O 3 is generally added for the polycondensation step) [ 30 , 31 , 34 , 35 , 36 , 48 , 58 , 59 , 102 ]. Dubois et al have synthesized a home-made titanium-silica complex that exhibited high catalytic activity [ 37 , 45 , 56 ].…”

“…Finally, vacuum is applied, and the temperature is increased for the polycondensation step. On the other hand, polylactide (PLA) or poly(ε-caprolactone) (PCL) oligomers can be prepared separately and added directly in a two-stage polymerization reaction [ 35 , 62 , 85 ].…”

High molecular weight poly(butylene terephthalate‐co‐butylene 2,5‐furan dicarboxylate) copolyesters: From synthesis to thermomechanical and barrier properties

“…2,5-FDCA was reported by Fittig and Heinzelmann as early as 1876. Currently, it has been regarded as a promising renewable alternative to TPA and many polyesters based on 2,5-FDCA, such as poly(ethylene furanoate) (PEF), [3,11,12] poly(propylene 2,5-furandicarboxylate) (PPF), [13,14] poly(butylene 2,5-furandicarboxylate) (PBF), [15][16][17][18] poly(octylene 2,5-furandicarboxylate) (POF), [19,20] poly(hexamethylene 2,5-furandicarboxylate) (PHF), [21] had been widely reported. Among them, the most studied one might be PEF because of its excellent thermomechanical properties and outstanding barrier to CO 2 and O 2 (19 and 11 times [22,23] to that of PET, respectively).…”