A Semicrystalline Furanic Polyamide Made from Renewable Feedstocks

Abstract

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.

Biobased Semi-Crystalline Polyesteramides from 2,5-Furandicarboxylic Acid and 5,5′-Isopropylidene Bis(2-furfurylamine): Synthesis toward Crystallinity and Chemical Stability

“…These peaks are associated to the polyester unit as evidenced, for example, in the poly­(1,6-hexylene 2,5-furandicarboxylate) XRD pattern, published elsewhere , and also in this work (Figure S5 of the Supporting Information). The diffractograms of the PEA incorporating higher amount of amide units (PEAF 3–4 ) display the main diffraction reflections peaks observed in the PEAF 1–2 patterns, at 2θ ∼17 and 24°, as well as several new sharp ones at 2θ ∼8, 9, 10, 12, 15, 22, and 30°, previously detected in furan-based polyamides, and these may arise from the establishment of a crystalline arrangement where the amide group, probably involved in intermolecular hydrogen bonds, plays a fundamental role. The degree of crystallinity ( X c ) values (Table ) clearly demonstrate the high crystallinity of these novel PEAFs, despite the fact that purely polyamide (PAF) was found to be an essentially amorphous displaying only a halo centered at 17° (Figure S6 of the Supporting Information).…”

Preparation of chemically recyclable bio-based semi-aromatic polyamides using continuous flow technology under mild conditions

“…It is reported that the furan ring facilitates the formation of intramolecular hydrogen bonds between the amide hydrogen atoms and oxygen atoms of the furan ring, thereby reducing the interchain hydrogen bonding interactions that are considered vital for the crystallization. 9,26 As shown in Fig. 4b, the glass transition temperature (T g ) decreases as the carbon chain length of the aliphatic segment in the diamine increases.…”

“…The molecular weights, thermal properties, and stability of the synthesized FPAs are comparable to those of their petrochemical counterparts. 9,10 This suggests that the FPAs have great potential to serve as bio-based replacements for traditional petroleum-based polyamides.…”

“…To date, only a small proportion of bio-based polymers are commercially available due to their inadequate properties and frequently higher production costs. 9 Melt polymerization is a commonly employed technique, but it necessitates that the monomers are able to form a stable melt. Synthesis of SAPs from diacids and diamines via polycondensation is conventionally carried out via a two-step synthesis procedure.…”

One‐pot Twostep Chemobiocatalytic Synthesis of a Furan Amino Acid from 5‐Hydroxymethylfurfural

“…5‐Formyl‐2‐furancarboxylic acid (FFCA) is one of intermediates in the successive oxidation of HMF into FDCA, [4] and its reductive amination can provide access to 5‐aminomethyl‐2‐furancarboxylic acid (AMFC), a furan‐containing amino acid [5] . Recently, Kanan and co‐workers reported a promising semicrystalline furanic polyamide material synthesized by AMFC polycondensation, [6] which has glass‐transition and melting temperatures comparable to that of commercial materials and higher than that of furanic semi‐aromatic polyamides ever reported. In addition, this chemical and derivatives could be used to produce furan‐based cyclic oligopeptides, [7] which are capable of selectively inhibiting the activity of telomerase, making them promising ligands for exploration for anticancer therapy.…”