Enzymatic synthesis of 2,5-furandicarboxylic acid-based semi-aromatic polyamides:enzymatic polymerization kinetics, effect of diamine chain length and thermal properties

• Published in: RSC Advances
• Main Authors: Jiang, Yi, Maniar, Dina, Woortman, Albert J. J., Loos, Katja
• Format: Article in Journal/Newspaper
• Language: English
• Published: 2016
• Subjects: LIPASE-CATALYZED SYNTHESIS; RENEWABLE RESOURCES; FURAN-2,5-DICARBOXYLIC ACID; ALIPHATIC POLYESTERS; BUILDING-BLOCK; DICARBONSAUREN; POLYMERS; MONOMERS; AMINES; UNITS; Antarc*; Antarctica
• Online Access: https://hdl.handle.net/11370/440ee0fe-571c-4c15-a971-a6d4b542b48d; https://research.rug.nl/en/publications/440ee0fe-571c-4c15-a971-a6d4b542b48d; https://doi.org/10.1039/c6ra14585j; https://pure.rug.nl/ws/files/49615010/Enzymatic_synthesis_of_2_5_furandicarboxylic_acid_based.pdf

2,5-Furandicarboxylic acid (FDCA)-based semi-aromatic polyamides are novel biobased alternatives to petrol-based semi-aromatic polyamides (polyphthalamides), that have a broad commercial interest as engineering thermoplastics and high performance materials. In this study, a series of FDCA-based semi-aromatic polyamides is successfully produced via Novozym (R) 435 (N435, an immobilized form of Candida antarctica lipase b (CALB))-catalyzed polycondensation of (potentially) biobased dimethyl 2,5-furandicarboxylate and aliphatic diamines differing in chain length (C4-C12), using a one-stage method at 90 degrees C in toluene. The obtained polyamides reach high weight-average molecular weights ranging from 15 800 to 48 300 g mol(-1); and N435 shows the highest selectivity towards 1,8-octanediame (C8). MALDI-ToF MS analysis indicates that no byproducts are formed during the enzymatic polymerization. Study of the kinetics of the enzymatic polymerization suggests that phase separation of FDCA-based oligoamides/polyamides takes place in the early stage of polymerization, and the isolated products undergo an enzyme-catalyzed solid-state polymerization. However, the isolation yields of the purified products from the enzymatic polymerizations are less than similar to 50% due to the production of a large amount of low molecular weight products that are washed away during the purification steps. Furthermore, the thermal properties of the enzymatic FDCA-based semi-aromatic polyamides are carefully investigated, and compared to those of the FDCA-based and petrol-based counterparts produced via conventional synthesis techniques as reported in literature.