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

Ragno, Daniele; Carmine, Graziano Di; Vannini, Micaela; Bortolini, Olga; Perrone, Daniela; Buoso, Sara; Bertoldo, Monica; Massi, Alessandro

doi:10.1039/d1py01687c

Cited by 11 publications

(15 citation statements)

References 65 publications

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“…The lack of clear end group peaks in the 1 H NMR spectra is consistent with the possibility of cyclic PAMF oligomers and may suggest that the cyclic oligomers are more easily solubilized than their longer linear counterparts. Cyclic oligomers of similar polymers have been identified before; − however, given their low molecular weight compared to the larger average absolute molecular weight identified by GPC, they are unlikely to be large components of this polymer sample.…”

Section: Resultsmentioning

confidence: 65%

A Semicrystalline Furanic Polyamide Made from Renewable Feedstocks

2022

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Semi-aromatic polyamides (SAPs) synthesized from petrochemical diacids and diamines are high-performance polymers that often derive their desirable properties from a high degree of crystallinity. Attempts to develop partially renewable SAPs by replacing petrochemical diacids with biobased furan-2,5-dicarboxylic acid (FDCA) have resulted in amorphous materials or polymers with low melting temperatures. Herein, we report the development of poly(5-aminomethyl-2-furoic acid) (PAMF), a semicrystalline SAP synthesized by the polycondensation of CO2 and lignocellulose-derived monomer 5-aminomethyl-2-furoic acid (AMF). PAMF has glass-transition and melting temperatures comparable to that of commercial materials and higher than that of any previous furanic SAP. Additionally, PAMF can be copolymerized with conventional nylon 6 and is chemically recyclable. Molecular dynamics (MD) simulations suggest that differences in intramolecular hydrogen bonding explain why PAMF is semicrystalline but many FDCA-based SAPs are not.

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Section: Resultsmentioning

confidence: 65%

A Semicrystalline Furanic Polyamide Made from Renewable Feedstocks

2022

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“…As 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) has been reported to be an effective organocatalyst for ROP of cyclic esters, [67][68][69][70][71][72][73][74][75][76] TBD-catalyzed ROP of monomers was first investigated in bulk conditions. The polymerization of DHB-Me with a [DHB-Me] : [TBD] : [I] ratio of 100 : 1 : 1 reached 71% conversion within 1 h at 70 °C (Table 1, entry 1).…”

Section: Resultsmentioning

confidence: 99%

Leveraging the monomer structure for high-performance chemically recyclable semiaromatic polyesters

Fan

Xing

et al. 2023

Polym. Chem.

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“…[29] By exploiting NHC catalysis Massi and co-workers developed the first organocatalytic procedure for the synthesis of hydroxymethylfuroate macrocyclic oligoesters 23 (Scheme 12). [28] The optimized reaction was carried out on HMF in Me-THF under high dilution conditions in the presence of oxidant quinone 15 affording mostly trimer and tetramer species of macrocycles in 77 % yield.…”

Section: Self-coupling and Umpolung Condensation Of Furaldehydes (Fa)smentioning

confidence: 99%

Organocatalytic Upgrading of Biomass Derived Building Blocks

Meninno

2023

Eur J Org Chem

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The depletion of finite primary fossil fuels we are facing makes necessary a deep metamorphosis in fundamental parts of the chemical industry. A progressive transition from petro‐based starting materials toward renewable biomass‐derived sources will have to take place in the synthesis of added‐value chemicals, important for our everyday life, such as pharmaceuticals, polymers, agrochemicals etc. Moreover, greener processes, carried out under friendlier reaction conditions, must be designed to address current concerns about the climate change and the resulting pressing need to reduce the environmental footprint of chemical processes. To this end, organocatalysis could offer a valuable opportunity for upgrading biomass‐derived platform molecules in line with the principles of Green Chemistry. This review presents some of recent and remarkable advancements in this emerging area. Organocatalysis has proven to be an efficient tool to transform low value bio‐based renewable platform building blocks into new high value bio‐based chemicals, with potential applications as synthetic intermediates, innovative materials and pharmaceutically active compounds.

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

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...

Cited by 11 publications

References 65 publications

A Semicrystalline Furanic Polyamide Made from Renewable Feedstocks

A Semicrystalline Furanic Polyamide Made from Renewable Feedstocks

Leveraging the monomer structure for high-performance chemically recyclable semiaromatic polyesters

Organocatalytic Upgrading of Biomass Derived Building Blocks

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