Enzymatic Synthesis of Copolyesters with the Heteroaromatic Diol 3,4-Bis(hydroxymethyl)furan and Isomeric Dimethyl Furandicarboxylate Substitutions.

Polyesters from furandicarboxylic acid derivatives, i.e., dimethyl 2,5-furandicarboxylate (2,5-DMFDCA) and 2,4-DMFDCA, show interesting properties among bio-based polymers. Another potential heteroaromatic monomer, 3,4-bis(hydroxymethyl)furan (3,4-BHMF), is often overlooked but holds promise for biopolymer synthesis. Cleaning and greening synthetic procedures, i.e., enzymatic polymerization, offer sustainable pathways. This study explores the Candida antarctica lipase B (CALB)-catalyzed copolymerization of 3,4-BHMF with furan dicarboxylate isomers and aliphatic diols. The furanic copolyesters (co-FPEs) with higher polymerization degrees are obtained using 2,4-isomer, indicating CALB's preference. Material analysis revealed semicrystalline properties in all synthesized 2,5-FDCA-based co-FPEs, with multiple melting temperatures (Tm) from 53 to 124 °C and a glass-transition temperature (Tg) of 9-10 °C. 2,4-FDCA-based co-FPEs showed multiple Tm from 43 to 61 °C and Tg of -14 to 12 °C; one of them was amorphous. In addition, all co-FPEs showed a two-step decomposition profile, indicating aliphatic and semiaromatic segments in the polymer chains.

Thiol-Ene Click Cross-linking of Starch Oleate Films for Enhanced Properties.

Biobased films were synthesized from starch oleate (DS = 2.2) cross-linked with polyethylene glycol with Mn = 2000 and 1000 g · mol-1, and ethylene glycol, all of which were esterified with either lipoic acid (LA) or 3-mercaptopropionic acid (MPA). Cross-linking was achieved through a UV-initiated thiol-ene click, and confirmed by Fourier transform infrared spectroscopy and rheometry. The films exhibit higher degradation temperatures, and an increased degree of crystallinity as cross-linker length increased. The introduction of MPA-based cross-linkers resulted in hydrophilic films, while the contact angle was barely affected by the addition of LA-based cross-linkers. A reduction in maximum strength upon introducing the cross-linkers was observed, while an increase in elongation was observed for most of the LA-based cross-linkers. Our results demonstrate the potential for tuning the mechanical and thermal properties of starch-based films through the cross-linker choice, with some formulations exhibiting increased flexibility that may be well suited for packaging applications.

Synthesis and Properties of Fully Biobased Crosslinked Starch Oleate Films.

Starch oleate (degree of substitution = 2.2) films were cast and crosslinked in the presence of air using UV curing (UVC) or heat curing (HC). A commercial photoinitiator (CPI, Irgacure 184) and a natural photoinitiator (NPI, a mixture of biobased 3-hydroxyflavone and n-phenylglycine) were used for UVC. No initiator was used during HC. Isothermal gravimetric analyses, Fourier Transform Infrared (FTIR) measurements, and gel content measurements revealed that all three methods were effective in crosslinking, with HC being the most efficient. All methods increased the maximum strengths of film, with HC causing the largest increase (from 4.14 to 7.37 MPa). This is consistent with a higher degree of crosslinking occurring with HC. DSC analyses showed that the Tg signal flattened as film crosslink densities increased, even disappearing in the case of HC and UVC with CPI. Thermal gravimetric analyses (TGA) indicated that films cured with NPI were least affected by degradation during curing. These results suggest that cured starch oleate films could be suitable for replacing the fossil-fuel-derived plastics currently used in mulch films or packaging applications.

Starch ester film properties: The role of the casting temperature and starch its molecular weight and amylose content.

Oleic acid and 10-undecenoic acid were used to esterify corn, tapioca, potato and a waxy potato starch, with a maximum degree of substitution of 2.4 and 1.9 respectively. The thermal and mechanical properties were investigated as a function of the amylopectin content and Mw of starch, and by the fatty acid type. All starch esters had an improved degradation temperature regardless of their botanical origin. While the Tg did increase with increasing amylopectin content and Mw, it decreased with increasing fatty acid chain length. Moreover, films with different optical appearances were obtained by varying the casting temperature. SEM and polarized light microscopy showed that films cast at 20 °C had porous open structures with internal stress, which was absent when cast at higher temperatures. Tensile test measurements revealed that films had a higher Young's modulus when containing starch with a higher Mw and amylopectin content. Besides that, starch oleate films were more ductile than starch 10-undecenoate films. In addition, all films were resistant to water at least up to one month, while some light-induced crosslinking took place. Finally, starch oleate films showed antibacterial properties against Escherichia coli, whereas native starch and starch 10-undecenoate did not.

A more efficient synthesis and properties of saturated and unsaturated starch esters.

This work presents a series of starch esters synthesized via 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD) catalyzed transesterifications in dimethyl sulfoxide (DMSO). The reaction was performed with saturated and unsaturated fatty acids (8, 11, and 18 carbon atoms). The degree of substitution (DS) was raised by purging the reaction flask with nitrogen instead of simply performing the reaction under a nitrogen atmosphere. The increase of DS was most obvious for long-chain fatty acids, as an almost complete DS was observed for starch stearate (2.8) and starch oleate (2.7). The products were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X-ray diffraction. Starch esters from unsaturated fatty acids have a lower Tg than their saturated analogues. Moreover, contact angle and moisture uptake measurements showed increased hydrophobicity for all starch esters in comparison to pristine starch. Our results show a more efficient method for synthesizing a biobased material that steers into the direction of a material that could replace conventional plastics.

Enzymatic Synthesis of Muconic Acid-Based Polymers: Trans, Trans-Dimethyl Muconate and Trans, ß-Dimethyl Hydromuconate.

The vast majority of commodity polymers are acquired from petrochemical feedstock, and these resources will plausibly be depleted within the next 100 years. Therefore, the utilization of carbon-neutral renewable resources for the production of polymers is crucial in modern green chemistry. Herein, we report an eco-friendly strategy that uses enzyme catalysis to design biobased unsaturated (co)polyesters from muconic acid derivatives. This method is an attractive pathway for the production of well-defined unsaturated polyesters with minimum side reactions. A suite of characterization techniques was performed to probe the reaction mechanism and properties of the obtained polyesters. It is rationalized that the alkene functionality of the muconate monomers plays an important role in the enzyme catalysis mechanism. The rendered polyesters possessed excellent thermal stabilities and unreacted alkene functionality that can consecutively undergo chain extension, copolymerization, or act as an anchor for other functional groups. These properties open new avenues in the fields of unsaturated polyester resins and photosensitive coatings.

Furan-Based Copolyesters from Renewable Resources: Enzymatic Synthesis and Properties.

Enzymatic polymerization provides an excellent opportunity for the conversion of renewable resources into polymeric materials in an effective and sustainable manner. A series of furan-based copolyesters was synthesized with M w ‾ up to 35 kg mol-1 , by using Novozyme 435 as a biocatalyst and dimethyl 2,5-furandicarboxylate (DMFDCA), 2,5-bis(hydroxymethyl)furan (BHMF), aliphatic linear diols, and diacid ethyl esters as monomers. The synthetic mechanism was evaluated by the variation of aliphatic linear monomers and their feed compositions. Interestingly, there was a significant decrease in the molecular weight if the aliphatic monomers were changed from diols to diacid ethyl esters. The obtained copolyesters were thoroughly characterized and compared with their polyester analogs. These findings provide a closer insight into the application of enzymatic polymerization techniques in designing sustainable high-performance polymers.

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

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.