Effects of Nonhydroxyl Oxygen Heteroatoms in Diethylene Glycols on the Properties of 2,5-Furandicarboxylic Acid-Based Polyesters

Abstract

With regard to polyesters based on biobased 2,5-furandicarboxylic acid (FDCA), our work presents a new strategy, heteroatom substitution, to adjust the thermal and gas barrier properties. The effects of nonhydroxyl oxygen heteroatoms in the diols on the properties of FDCA-based polyesters were first investigated by a combination of an experiment and molecular simulation. The results demonstrated that the introduction of oxygen heteroatoms significantly influenced the thermal and gas barrier properties. As for the two model polymers with a very similar skeleton structure, poly­(pentylene 2,5-furandicarboxylate) (PPeF) and poly­(diethylene glycol 2,5-furandicarboxylate) (PDEF), their T g exhibited an obviously increasing order. Moreover, they showed similar thermal stability and thermal oxidative stability. Dynamic mechanical analysis, positron annihilation lifetime spectroscopy, and molecular dynamics simulation indicated that the gas barrier properties followed the sequence of PDEF > PPeF mainly due to the decreased chain mobility and smaller fractional free volume. In-depth analysis of the effects of heteroatom substitution has an important directive significance for the design and preparation of new high glass transition temperature or novel excellent gas barrier materials. Through the manipulation of different heteroatoms in the diols, the polyesters with varied properties can be expected.

Melt polycondensation of 2,5-tetrahydrofurandimethanol with various dicarboxylic acids towards a variety of biobased polyesters

“…The mechanical properties of PDEGF were basically consistent with those reported in the literature. 57 In conclusion, as diols in homopolyesters were changed from DEG to THFDM, their strength was significantly improved (as shown in Fig. 8(b)).…”

A synchronously chemically closed-loop and high-performance approach for furan-based copolyesters with robustness, high gas barriers, and high puncture resistance

“…This result is due to the relatively large electronegativity of the O atoms affecting the rigidity and polarity, which inhibit the movement and rotation of the polymer chains. 44,45 In addition, the low F V value of PBD y F can also obstruct the passage of gas molecules and enhance the gas barrier properties which is shown in the next section.…”

Effects of Different Isomers of Thiophenedicarboxylic Acids on the Synthesis and Properties of Thiophene-Based Sustainable Polyesters

“…The synthetic method of polyesters in this work was similar to that previously described in the literature by our research group. 11 In brief, the polyesters were synthesized via a two-step procedure by directesterification between diacids (34.43 g, 0.2 mol) and a little excess of diols (21.63 g, 0.24 mol) under the protection of a N 2 atmosphere at 160−200 °C and then melt polycondensation assisted by the catalyst of tributyltin (TBT, 136 μL, 0.2 mol % based on the amount of diacids) under reduced pressure (below 50 Pa) at 210−225 °C. Low reaction temperatures were favored in the esterification step to reduce the adverse effect of decarboxylation.…”

“…Under the current background of global carbon emission reduction and the progressive depletion of fossil resources, the development of biobased polymer materials is facing unprecedented opportunities and challenges. − As a very important class of polymers, polyesters are widely used in daily life due to their significant advantages such as light weight, ease of processing and large-scale production, and low cost. Aromatic structural units usually have a critical impact on the thermal-mechanical properties and functions of polyesters. − However, only a few biobased aromatic monomers have been reported up to now. − One of the most widely studied examples so far is 2,5-furandicarboxylic acid (2,5-FDCA), a cyclic biobased monomer whose production relies heavily on sugars, which was selected as the only aromatic diacid of the top twelve value-added biobased platform chemicals by the U.S. Department of Energy. , It has been considered a highly promising candidate for a biobased replacement of petroleum-based terephthalic acid (TPA) and has aroused tremendously growing interest from both academia and industry. − The introduction of 2,5-FDCA structural units helps to enhance the glass-transition temperature, chemical stability, and mechanical properties (e.g., mechanical modulus and strength) of polyesters. The emerging need of the next-generation sustainable high-performance bioplastics has significantly promoted the development of novel biobased aromatic monomers completely decoupled from fossil resources.…”