Lipase‐Catalyzed Synthesis of Furan‐Based Oligoesters and their Self‐Assembly‐Assisted Polymerization

Abstract

We investigate the synthesis of bio-based hydrophilic and hydrophobic oligoesters, which in turn are derived from easily accessible monomers from natural resources. In addition to the selection of renewable monomers, Novozyme 435, an immobilized lipase B from Candida antarctica was used for the oligomerization of monomers. The reaction conditions for oligomerization using Novozyme 435 were established to obtain a moderate-to-good yield. The average number of repeating units and the molecular weight distribution of hydrophilic and hydrophobic oligoester were identified by using NMR spectroscopy, gel-permeation chromatography, and MS. The oligoester derived from a hydrophilic monomer self-assembled to form a viscous solution, which upon further heating resulted in the formation of a polymer by the intermolecular Diels-Alder reaction. The viscosity of the solution and the assembly of oligoester to form a fibrous structure were investigated by using rheological studies, XRD, and SEM. The molecular weight of the cross-linked polymer was identified by using matrix-assisted laser desorption/ionization-MS. The thermal properties of the bio-based polymers were investigated by using thermogravimetric analysis and differential scanning calorimetry. For the first time, the self-assembly-assisted polymerization of an oligoester is reported using the intermolecular Diels-Alder reaction, which opens a new avenue in the field of polymer science.

Renewable Responsive Systems Based on Original Click and Polyurethane Cross‐Linked Architectures with Advanced Properties

“…More recently, Muthusamy et al. used the same enzymatic catalyst to obtain furan‐based oligoesters . The use of enzymes as green catalysts for macromolecular synthesis has become prevalent in the recent years, as highlighted by Kobayashi and co‐workers .…”

“…[28] Nevertheless, this esterification reaction can also be accomplished by using Candida antarctica lipase B, an enzymatic catalyst, withg reener conditions, as explored by Sengupta et al [29] More recently,M uthusamy et al used the same enzymatic catalystt oo btain furan-based oligoesters. [30] The use of enzymes as green catalysts for macromolecular synthesis has become prevalent in the recent years, as highlighted by Kobayashi and co-workers. [31] The FTIR spectrum of FMO exhibits ap redominant band at ñ = 1738cm À1 ,w hich confirms the presence of an ester carbonyl group, and furan heterocycle bands at ñ = 1503, 1375, 1347, 1228, 1080, 920, 885, 739, and 599 cm À1 (Figure 1).…”

Biotic and Abiotic Synthesis of Renewable Aliphatic Polyesters from Short Building Blocks Obtained from Biotechnology

“…Many of them are actually used for industrial production in the food, pharmacology,m edicine, and textile industries. [176][177][178] One of the limiting factors in the use of enzymesi nc hemistry,e specially for polymer synthesis, is their low stability at high temperatures andi no rganic solvents, which are often required to dissolve some chemicalc ompounds. [174] The concept of green chemistry andi ts principles are now well known, since Anastas and Warner introduced the idea of sustainability into modernc hemistry.…”

“…Moreover,i n some cases,e nzymesa re robust enough to be used in combination with other chemical catalystsf or new chemoenzymatic processes. [176][177][178] One of the limiting factors in the use of enzymesi nc hemistry,e specially for polymer synthesis, is their low stability at high temperatures andi no rganic solvents, which are often required to dissolve some chemicalc ompounds. Onew ay to improve enzyme stabilityi no rganic solvents is immobilization.…”

Lipase-catalyzed synthesis and post-polymerization modification of new fully bio-based poly(hexamethylene γ-ketopimelate) and poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) copolyesters

“…Liese and co-workers developed enzyme-catalyzed synthesis of a new bio-based polyester from Pripol 1012 and 1,3-propanediol (42). Moreover, several bio-based functional polyesters including furan- (43,44), sorbitol-(45), glucose- (46), itaconate- (47,48), and castor oil-based polyesters (49,50) were obtained through the CALB-catalyzed polymerization. Nevertheless, only a few studies on the biocatalytic synthesis of PKEs are reported (51)(52)(53).…”