Partially Renewable Poly(butylene 2,5-furandicarboxylate-co-isophthalate) Copolyesters Obtained by ROP

Abstract

Cyclic butylene furandicarboxylate (c(BF) n ) and butylene isophthalate (c(BI) n ) oligomers obtained by high dilution condensation reaction were polymerized in bulk at 200 • C with Sn(Oct) 2 catalyst via ring opening polymerization to give homopolyesters and copolyesters (coPBF x I y ) with weight average molar masses in the 60,000-70,000 g·mol −1 range and dispersities between 1.3 and 1.9. The composition of the copolyesters as determined by NMR was practically the same as that of the feed, and they all showed an almost random microstructure. The copolyesters were thermally stable up to 300 • C and crystalline for all compositions, and have T g in the 40-20 • C range with values decreasing almost linearly with their content in isophthalate units in the copolyester. Both melting temperature and enthalpy of the copolyesters decreased as the content in butylene isophthalate units increased up to a composition 30/70 (BF/BI), at which the triclinic crystal phase made exclusively of butylene furanoate units changed to the crystal structure of PBI. The partial replacement of furanoate by isophthalate units decreased substantially the crystallizability of PBF.

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

“…The research group of Dr. Muñoz-Guerra has synthesized various furanoate-containing cyclic oligomers (mixtures of dimers, trimers, and tetramers mainly) and copolymerized them by entropically-driven ROP ( Scheme 2 ) [ 64 , 66 , 69 , 83 , 86 , 105 ]. One of the advantages of ROP is the high polymerization rate, which results in relatively milder conditions and shorter reaction times compared to traditional two-step melt polycondensations.…”

Investigation of the catalytic activity and reaction kinetic modeling of two antimony catalysts in the synthesis of poly(ethylene furanoate)

“…[36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52] The extended research on furan-based polyesters has resulted in a variety of starting monomers and polymerization techniques that can be employed for their synthesis. 12,22,[53][54][55][56][57][58][59][60][61][62][63][64][65][66][67] Nevertheless, until now, the most popular strategy is utilizing dimethyl 2,5-furandicarboxylate (DMFD) in traditional melt polycondensations. Several catalytic systems have been screened for the polycondensation of DMFD by different research groups, and titanium catalysts exhibited the highest catalytic activity.…”

Organocatalytic synthesis of poly(hydroxymethylfuroate) via ring-opening polymerization of 5-hydroxymethylfurfural-based cyclic oligoesters

“…Remarkably, the optimized process could be scaled up to 6.5 mmol of HMF affording c (HMF) n in 77% yield (entry 7), this value being in line with previous HDC studies. 8 a ,9,15 a , b In this gram-scale experiment, Me-THF was easily recovered by distillation and the diol 2′ separated and reoxidized to 2 with air in the presence of catalytic phthalocyanine (see the Experimental section).…”

“…6 Furanic PEs are usually produced by melt polycondensation or polytransesterification; 4 a ,5,7 however, the severe reaction conditions (eventually causing polymer discoloration/degradation), the need for by-product removal, and the moderate molecular weights may represent important limitations of those approaches in some occasions. Very recently, thanks to the pioneering studies of Morbidelli 8 and Muñoz-Guerra groups, 9 the entropically driven ring-opening polymerization (ED-ROP) 10 of furan-based macrocyclic oligoesters (MCOs) has emerged as an alternative strategy to access a variety of poly(alkylene 2,5-furandicarboxylate)s with high efficiency. While the ROP of small-to-medium size cyclic oligoesters takes place by the relief of the ring strain, the ROP of MCOs proceeds without enthalpy exchange and it is mainly driven by entropy.…”