Aromatic But Sustainable: Poly(butylene 2,5-furandicarboxylate) as a Crystallizing Thermoplastic in the Bioeconomy

Abstract

Aliphatic/aromatic thermoplastic polyesters are a very interesting family of polymers with many applications. Poly(alkylene 2,5-furandicarboxylate)s (PAF)s are the biobased alternatives to poly(alkylene terephthalate)s and are expected to play a key role in bioeconomy. The most important PAFs are poly(ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5furandicarboxylate) (PPF), and poly(butylene 2,5-furandicarboxylate) (PBF), which crystallize slowly. PBF shows a typical PAF thermal behavior but a little faster crystallization compared to that of PPF and PEF. PBF was used in this work as a model material to understand the key parameters of the solidification of PAFs during processing. A detailed study of the kinetics of isothermal and dynamic melt and cold crystallization of PBF at very slow and moderate cooling and heating rates (0.1−20 °C/min) was carried out. Multiple melting was also analyzed. The equilibrium melting temperature was determined (T m o = 196.4 °C). The activation energy of non-isothermal crystallization from the melt decreased with increasing the cooling rate, in accordance with an increasing crystallization rate with supercooling. The cold-crystallization rate increased with increasing the difference between the cold-crystallization temperature (T cc ) and the glass transition temperature (T g ), which in turn increased with the heating rate. Several theoretical models were elaborated for the treatment of the crystallization data. Polarized optical microscopy revealed the formation of ring-banded spherulites at elevated temperatures (T c )s.

Directional Epitaxy Intensifying Intermolecular =C–H···O=C Hydrogen Bonding to Expedite Bulk Crystallization of Biobased Poly(butylene 2,5-furandicarboxylate)

“…As contrastively analyzed in the Supporting Information with Tables S1 and S2, the data fitted in 3–50% are most accurate for PBF due to the high R 2 values, and the resultant Avrami parameters are summarized in Table . For pure PBF, the Avrami index n is 2.50 and 2.59 for its crystallization at 130 and 140 °C, respectively, close to the past reported 2.40 at 135–142.5 °C, but it decreases to 2.16 at 150 °C, perhaps meaning the dimensional transition from spherulites to axialites at high T c . With NA, the n reduces to ∼2 and ∼2.3 at 130 and 140 °C, respectively, which was generally attributed to the formation of a large number of nuclei at the polymer/filler interface. , It is then reasonable that the n of ∼2 implies a high possibility of two-dimensional nucleation of PBF upon the NA surface.…”

Recent Progress on Sustainable 2,5-Furandicarboxylate-Based Polyesters: Properties and Applications

“…Additionally, PEF presented excellent gas barrier features in comparison with PET and superior mechanical and thermal resistance, but it exhibited a brittle characteristic at room temperature. Furthermore, various PAFs homopolyesters composed of different aromatic diols were prepared as well, such as poly(butylene 2,5-furandicarboxylate) (PBF), − poly(propylene 2,5-furandicarboxylate) (PPF), ,− poly(nonylene furandicarboxylate) (PNF), ,− poly(hexamethylene 2,5-furandicarboxylate) (PHF), , poly(octylene 2,5-furandicarboxylate) (POF or P8F), poly(1,4-cyclohexanedimethylene furandicarboxylate) (PCF), poly(decylene furandicarboxylate) (PDF), , poly(trimethylene 2,5-furanoate) (PTF), , poly(hexamethylene diglycolate) (PHDG), poly(hexamethylene furanoate) PHF–OH, poly(triethylene furanoate) PTEF–OH, poly(ethylene- co -1,4-cyclohexanedimethylene 2,5-furandicarboxylate) (PECF), , poly(ethylene- co -hexamethylene 2,5-furandicarboxylate) (PEHF), poly(ethylene 2,5-thiophenedicarboxylate) (PETF), poly(ethylene- co -propylene furandicarboxylate) (PEPF), poly(butylene adipate- co -butylene furandicarboxylate) (PBAF), − poly(butylene- co -1,4-cyclohexanedimethylene 2,5-furandicarboxylic acid) (PBCFs), ,, poly(1,4-butanediol 2,5-thiophenedicarboxylate) (PBTF), ,,, poly(decylene 2,5-furandicarboxylate) (PDeF or P10F), poly(dodecylene 2,5-furandicarboxylate) (PDoF or P12F), poly(decylene terephthalate- co -decylene furandicarboxylate) (PDTF), poly(pentylene furandicarboxylate) (PPeF), , poly(propylene 2,5-thiophenedicarboxylate) (PPTF), poly(heptylene furandicarboxylate) (PHepF), poly(hexamethylene 2,5-furandicarboxylate) (PHFC), poly(trimethylene 1,4-cyclohexanedicarboxylate) (PTCE), poly(neopentyl 1,4-cyclohexanedicarboxylate) (PNCE), poly(propylene cyclohexanedicarboxylate) (PPCE),…”

2,5-Tetrahydrofurandimethanol as a sustainable comonomer for modification of polyethylene terephthalate: Liter-level pilot test and non-isothermal crystallization kinetics

“…Ether linkages gave strong polarity, hydrophilicity, and biocompatibility to polyesters, and nonlinear structure was more rigid that produced high T g and great mechanical properties. [28][29][30] In this study, THFDM was introduced into the PET as a sustainable copolymer monomer to synthesize poly (ethylene-co-tetrahydrofurandimethanol terephthalate) (PETT) for replacing the previous role of CHDM or IPA. Due to the high price of THFDM, only a small amount (≤6 mol%) of THFDM was added during copolymerisation to design a new sustainable copolyester with similar properties to PET but with easier processing and less crystallization activity.…”