Poly(ethylene furanoate- co -ethylene terephthalate) biobased copolymers: Synthesis, thermal properties and cocrystallization behavior

Κωνσταντοπούλου, Μαρία; Terzopoulou, Zoi; Nerantzaki, Maria; Tsagkalias, John; Achilias, Dimitris S.; Bikiaris, Dimitrios N.; Exarhopoulos, Stylianos; Papageorgiou, Dimitrios G.; Papageorgiou, George Z.

doi:10.1016/j.eurpolymj.2017.02.037

Cited by 94 publications

(96 citation statements)

References 82 publications

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“…The first two polyesters (PEF, PPF) show excellent gas barrier, mechanical and thermal properties, superior than those of the corresponding polyesters based on terephthalic acid, poly(ethylene terephthalate) (PET), and poly(propylene terephthalate) (PPT) . There exist few studies on copolymers and nanocomposites based on PEF, PPF, and PBF, as well as a few PAFs . Surprisingly, blends of these compounds attracted much less attention (to the best of our knowledge, only two studies reported on PBF/PLA blends).…”

Section: Introductionmentioning

confidence: 99%

Sustainable Polymers from Renewable Resources: Polymer Blends of Furan‐Based Polyesters

Poulopoulou

Kasmi

Bikiaris

et al. 2018

Macro Materials & Eng

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A series of blends of furan‐based green polyesters, for eco‐friendly packaging materials, are synthesized. Poly(ethylene 2,5‐furandicarboxylate) (PEF), poly(propylene 2,5‐furandicarboxylate) (PPF), and poly(butylene 2,5‐furandicarboxylate) (PBF) are synthesized by applying melt polycondensation. Blends of the above polyesters with 50/50 w/w composition as well as blends of furanoate/terephthalate (PPF/PPT) are also prepared. The glass temperature along with the crystallization and melting behaviors of melt quenched blends are studied aiming at understanding their dynamic state and miscibility. Based on their Tg and crystallization behavior, PEF/PPF shows dynamic homogeneity and miscibility whereas PPF/PBF and PEF/PBF exhibit partial miscibility and immiscibility, respectively. In an effort to dynamically homogenize the compounds, reactive blending is applied and the behavior of the resulting blends is monitored following quenching. A profound improvement in blend homogenization is observed with increasing melt mixing time for the PPF/PPT sample, evidenced by the single glass temperature and by the narrowing in liquid‐to‐glass regime. The obtained single glass temperature together with the suppressed tendency for crystallization with increasing mixing time are taken as evidences of dynamic and thermodynamic homogeneity.

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Section: Introductionmentioning

confidence: 99%

Sustainable Polymers from Renewable Resources: Polymer Blends of Furan‐Based Polyesters

Poulopoulou

Kasmi

Bikiaris

et al. 2018

Macro Materials & Eng

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“…The pseudo-eutectic behavior of isodimorphic polymers is manifested by a decrease in the transition temperatures with composition departing from those of the two homopolyesters, until a minimum value is reached. The comonomer concentration at which this minimum is found is generally located around the equimolar composition [20,21], however, some systems show pseudo-eutectic points in significantly different concentration interval (e.g., 60:40, 80:20) [4,11,13,16,19,23,36,37]. For instance, in poly (hexamethylene dicarboxilate) copolymers the eutectic composition shifts from a co-unit concentration of 50 to 20 %, with increasing the length of aliphatic diacid units from 4 to 8 CH 2 units [11].…”

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confidence: 99%

“…For instance, in poly (hexamethylene dicarboxilate) copolymers the eutectic composition shifts from a co-unit concentration of 50 to 20 %, with increasing the length of aliphatic diacid units from 4 to 8 CH 2 units [11]. In most studies [4,11,16,19,21,36], the minimum of crystallization/melting temperature is located at compositions shifted towards higher contents of the commoner whose respective homopolyester has the lower melting point.…”

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“…Flory, Baur, Sanchez-Eby and Wendling-Suter equations have been employed to describe the experimental variation of equilibrium melting temperatures of isodimorphic copolyesters in several studies [4,9,11,36]. As an example, Figure 13 shows comparison performed for copolyesters of hexamethylene diol with diacids of different lengths with the different models [11].…”

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Crystallization of isodimorphic aliphatic random copolyesters: Pseudo-eutectic behavior and double-crystalline materials

Pérez-Camargo

Arandia

Safari

et al. 2018

European Polymer Journal

161

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Isodimorphic random copolyesters are intriguing polymeric materials that can crystallize in their entire composition range, despite the random distribution of comonomer units along their chains. This behavior stems from the relatively similar chemical repeating units of the parent homopolymers. In this feature article, we review our recent works on isodimorphic aliphatic copolyesters, and extract general trends in the framework of the literature. Isodimorphic behavior is a complex phenomenon driven by comonomer partition within the crystalline unit cells formed. These copolyesters crystallize in the entire composition range displaying a pseudo-eutectic behavior when their melting points are plotted as a function of composition. Two crystalline phases, which resembled the crystalline structures of the parent homopolymers, are formed, depending on the considered composition range. The unit cell dimensions of the parent homopolymers change, as a consequence of the inclusion of co-units. At the pseudo eutectic point or pseudo-eutectic region, two crystalline phases can co-exist and their formation strongly depends on thermal history. In this case, double crystalline random copolyesters with two melting points and mixed double-crystalline spherulites can be obtained. The exact composition of the pseudo-eutectic point, the level of comonomer inclusion and the crystallinity degrees cannot be easily predicted by the copolyester chemical structure and composition. These are important issues for further future studies, as well as the quantitative determination of comonomer inclusion in the generated crystalline phases. The extraordinary variation of thermal properties, morphology and crystallinity that isodimorphic random copolyesters display as a function of composition, allows to conveniently tailor their biodegradation, permeability to gases and mechanical properties.

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“…These are copolymerization, incorporation of additives resulting in composite or nanocomposite materials, or blending with other polymers. The synthesis of a series of furan-based copolymers has been reported in literature [43][44][45][46][47][48][49][50]. Furthermore, some recent works reported PEF, PPF and PBF nanocomposites [51][52][53][54][55].…”

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Sustainable Plastics from Biomass: Blends of Polyesters Based on 2,5-Furandicarboxylic Acid

et al. 2020

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Intending to expand the thermo-physical properties of bio-based polymers, furan-based thermoplastic polyesters were synthesized following the melt polycondensation method. The resulting polymers, namely, poly(ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), poly(butylene 2,5-furandicarboxylate) (PBF) and poly(1,4-cyclohexanedimethylene 2,5-furandicarboxylate) (PCHDMF) are used in blends together with various polymers of industrial importance, including poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), poly(L-lactic acid) (PLA) and polycarbonate (PC). The blends are studied concerning their miscibility, crystallization and solid-state characteristics by using wide-angle X-ray diffractometry (WAXD), differential scanning calorimetry (DSC) and polarized light microscopy (PLM). PEF blends show in general dual glass transitions in the DSC heating traces for the melt quenched samples. Only PPF–PEF blends show a single glass transition and a single melt phase in PLM. PPF forms immiscible blends except with PEF and PBF. PBF forms miscible blends with PCHDMF and PPF, whereas all other blends show dual glass transitions in DSC and phase separation in PLM. PCHDMF–PEF and PEN–PEF blends show two glass transition temperatures, but they shift to intermediate temperature values depending on the composition, indicating some partial miscibility of the polymer pairs.

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Poly(ethylene furanoate- co -ethylene terephthalate) biobased copolymers: Synthesis, thermal properties and cocrystallization behavior

Cited by 94 publications

References 82 publications

Sustainable Polymers from Renewable Resources: Polymer Blends of Furan‐Based Polyesters

Sustainable Polymers from Renewable Resources: Polymer Blends of Furan‐Based Polyesters

Crystallization of isodimorphic aliphatic random copolyesters: Pseudo-eutectic behavior and double-crystalline materials

Sustainable Plastics from Biomass: Blends of Polyesters Based on 2,5-Furandicarboxylic Acid

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