The synthesis of hydroxymethylfuroate macrocyclic oligoesters c(HMF)(n) promoted by an N-heterocyclic carbene (NHC) organocatalyst is herein presented together with the subsequent organocatalytic, entropically-driven ring-opening polymerization (ED-ROP) leading to the fully furan-based poly(hydroxymethylfuroate) (PHMF). The target macrocycles (mostly trimer and tetramer species) have been obtained directly from the platform chemical HMF (77% isolated yield) under high dilution conditions using a quinone as the external oxidant and the green solvent Me-THF. The ED-ROP of c(HMF)(n) has been optimized at 160 degrees C (melt condensation technique) with the couple triazabicyclodecene (TBD)/n-octanol (1 : 1) as catalyst/initiator of the polymerization process in the presence of commercial antioxidants Irganox 1010 (0.1% w/w) and Irgafos 126 (0.3% w/w) to suppress degradation side reactions. Under these conditions, the bio-based PHMF (poly-HMF) was obtained as a color-free polymer with number-average molecular weight up to 48 600 g mol(-1) and dispersity between 1.5 and 1.9 as determined by NMR and GPC analyses. The thermal behavior of the novel furan-based polyester PHMF was investigated (TGA and DSC analyses) observing a good thermal stability (onset temperature of degradation similar to 310 degrees C) and a semicrystalline structure with melting temperature above 160 degrees C when processed from solvent, thus making PHMF a promising material for processing as other commercial polyesters.

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

Ragno, Daniele
Primo
;
Di Carmine, Graziano
Secondo
;
Bortolini, Olga;Perrone, Daniela;Buoso, Sara;Bertoldo, Monica
Penultimo
;
Massi, Alessandro
Ultimo
2022

Abstract

The synthesis of hydroxymethylfuroate macrocyclic oligoesters c(HMF)(n) promoted by an N-heterocyclic carbene (NHC) organocatalyst is herein presented together with the subsequent organocatalytic, entropically-driven ring-opening polymerization (ED-ROP) leading to the fully furan-based poly(hydroxymethylfuroate) (PHMF). The target macrocycles (mostly trimer and tetramer species) have been obtained directly from the platform chemical HMF (77% isolated yield) under high dilution conditions using a quinone as the external oxidant and the green solvent Me-THF. The ED-ROP of c(HMF)(n) has been optimized at 160 degrees C (melt condensation technique) with the couple triazabicyclodecene (TBD)/n-octanol (1 : 1) as catalyst/initiator of the polymerization process in the presence of commercial antioxidants Irganox 1010 (0.1% w/w) and Irgafos 126 (0.3% w/w) to suppress degradation side reactions. Under these conditions, the bio-based PHMF (poly-HMF) was obtained as a color-free polymer with number-average molecular weight up to 48 600 g mol(-1) and dispersity between 1.5 and 1.9 as determined by NMR and GPC analyses. The thermal behavior of the novel furan-based polyester PHMF was investigated (TGA and DSC analyses) observing a good thermal stability (onset temperature of degradation similar to 310 degrees C) and a semicrystalline structure with melting temperature above 160 degrees C when processed from solvent, thus making PHMF a promising material for processing as other commercial polyesters.
2022
Ragno, Daniele; Di Carmine, Graziano; Vannini, Micaela; Bortolini, Olga; Perrone, Daniela; Buoso, Sara; Bertoldo, Monica; Massi, Alessandro
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11392/2478225
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