Organocatalytic synthesis of poly(hydroxymethylfuroate) via ring-opening polymerization of 5-hydroxymethylfurfural-based cyclic oligoesters†‡
*a
Graziano
Di Carmine,
a
Micaela
Vannini,
b
Olga
Bortolini,
c
Daniela
Perrone,
c
Sara
Buoso,
d
Monica
Bertoldo
a
and
Alessandro
Massi
*a
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 °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 ∼310 °C) and a semicrystalline structure with melting temperature above 160 °C when processed from solvent, thus making PHMF a promising material for processing as other commercial polyesters.
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