Enzymatic Polymerization of Dimethyl 2,5-Furandicarboxylate and Heteroatom Diamines

Abstract

Previously, we have synthesized a diverse range of 2,5-furandicarboxylic acid (FDCA)-based semiaromatic polyamides via enzymatic polymerization. This novel class of polymers are biobased alternatives to polyphthalamides, which are petrol-based semiaromatic polyamides. From a commercial perspective, they have interesting properties as high-performance materials and engineering thermoplastics. It is even more appealing to explore novel FDCA-based polyamides with added functionality, for the development of sustainable functional materials. Here, a set of FDCA-based heteroatom polyamides have been successfully produced via Novozyme 435 (N435)-catalyzed polymerization of biobased dimethyl 2,5-furandicarboxylate with (potentially)heteroatom diamines, namely, 4,9-dioxa-1,12-dodecanediamine (DODA), diethylenetriamine, and 3,3-ethylenediiminopropylamine. We performed the enzymatic polymerization in solution and bulk. The latter approach is more sustainable and results in higher molecular weight products. Among the tested heteroatom diamines, N435 shows the highest catalytic activity toward DODA. Furthermore, we find that all obtained FDCA-based heteroatom polyamides are amorphous materials with a relatively high thermal stability. These heteroatom polyamides display a glass-transition temperature ranging from 41 to 107 °C.

Novozym 435: the “perfect” lipase immobilized biocatalyst?

“…2,5-Furandicarboxylic acid-based semi-aromatic polyamides have been produced via polymerization of dimethyl 2,5-furandicarboxylate catalyzed by N435. 367 In other instances, glycerol based polymers are produced. For example, N435 was used to produce polyglycerol fatty acid esters of different-chain-length fatty acids in a solventfree system.…”

Creating Diversity from Biomass: A Tandem Bio/Metal‐Catalysis towards Chemoselective Synthesis of Densely Substituted Furans

“…Recently, implementation of biocatalysis in sustainable chemistry has allowed researchers to address and bypass several drawbacks of the analogous chemical reactions, such as low yields, harsh conditions, laborious purification steps, long operating times, high production costs, and waste . In particular, lipases have been extensively employed in enzymatic resolutions and for the generation of biobased polyamide polymers, namely those based on FDCA and its dimethyl and diethyl esters (Scheme ) . Additionally, Candida Antarctica Lipase B (CAL B)‐ and cross‐linked enzyme aggregate lipase (CLEA)‐catalyzed monoamidation of terephthalates has been reported .…”

Thermal cross‐link between 2,5‐furandicarboxylic acid‐based polyimides and bismaleimide via Diels–Alder reaction

“…To date, the research and commercialization of 2,5-FDCA derived from biomass 5-hydroxymethylfurfural (HMF) have been largely developed. [6,7] A variety of 2,5-FDCA-based plastics, including polyesters, [8][9][10] polyamides, [11][12][13][14] and polyurethanes, [15] have shown thermal and mechanical properties similar to their TPA/IPA counterparts. However, low-glass transition temperatures (T g s) ≤ 180 o C and melting temperatures (T m s) ≤ 215 o C of 2,5-FDCA-based plastics limited their applications as high-performance materials.…”