Development of High-Molecular-Weight Fully Renewable Biopolyesters Based on Oxabicyclic Diacid and 2,5-Furandicarboxylic Acid: Promising as Packaging and Medical Materials

Abstract

Renewable and biodegradable linear polyesters with oxabicyclic units based on the ring-opening polymerization (ROP) have attracted considerable interest as alternatives to petrochemical-based polyesters. However, incorporating bio-based aromatic building blocks into the linear polyesters with oxabicyclic units by the ROP process is limited. Herein, we report three series of oxabicyclic renewable polyesters based on oxabicyclic diacid (OBDA), monomethyl oxabicyclic diacid (MBDA), and oxabicyclic anhydride with dimethyl substituents (d-MBDA) derived from bio-based furanics and synthesized via melt polymerization (MP). The molecular weights of the polyesters obtained from OBDA were significantly higher than those of the reported polyesters based on OBDA anhydride derivatives, leading to significantly higher glass-transition temperature (T g ) values and tensile strength. Furthermore, a series of fully bio-based copolyesters (PBOB m F n ) was first obtained via the MP strategy by the incremental replacement of OBDA with bio-based 2,5-furandicarboxylic acid (FDCA). The incorporation of FDCA units significantly improved the thermal stabilities and mechanical properties of the linear polyesters with oxabicyclic units and endowed them with gas barrier properties that were better than those of commercial poly(ethylene terephthalate) (PET). The T g values of PBOB m F n ranged from 38.8 to 40.8 °C and were comparable with that of the commercial biomedical material Vicryl. Additionally, the trade-off between OBDA and FDCA units can control the fast biodegradation and environmental durability of the PBOB m F n polyester series. PBOB m F n also showed excellent biocompatibility to and was safe for both RAW264.7 and PC12 cells. The strategy of the incorporation of FDCA building blocks via MP enhanced the comprehensive properties of the linear polyesters with oxabicyclic units; moreover, the adjustment between FDCA and OBDA units can be leveraged to control the polyester roles between packaging and biomedical fields while retaining the completely renewable nature of the parent of polyesters.

Xylose-Based Polyethers and Polyesters Via ADMET Polymerization toward Polyethylene-Like Materials

“…In the latter polymer, ether linkages are thought to be responsible for increasing chain flexibility and decreasing crystallinity, leading to a higher gas permeation. , The presence of an oxygenated heterocycle moiety in poly­(2a)-H , disrupting chain packing, is most likely to have the same effect here and cause poly­(2a)-H to have slightly increased permeability values relative to lcAPES PES-X,5 (X = 10–16) reported by Zhou et al (0.6–1.0 barrer) . Despite having slightly higher permeability values than other bioderived polymers, including outside the lcAPES category, − there might be a potential to further increase barrier properties of this polymer through processing, by orientating polymer chains to reduce the free volume and enhance crystallinity. An alternative approach could involve the removal of some isopropylidene groups from the xylose cores, so as to induce intermolecular hydrogen bonding and increase crystallinity. , …”

Recent Progress on Bio-Based Polyesters Derived from 2,5-Furandicarbonxylic Acid (FDCA)

“…Weinberger et al [ 118 ] investigated the PEF enzymatic degradation and found that the influence of particle size became smaller when the molecular weight was higher and they optimized the hydrolysis conditions such as in the 1 M phosphate buffer, pH 8, at 65 °C with Humicola insolens , where PEF reached 100% hydrolysis. Zhou et al [ 119 ] synthesized a series of biodegradable polyesters with FDCA, BDO, and oxabicyclic units via ROP. The polyesters obtained showed biodegradability within seven days with less than 30 mol% FDCA units.…”

The Interplay between Kinetics and Thermodynamics in Furan Diels–Alder Chemistry for Sustainable Chemicals Production

“…Kinetically blocking the reverse DA process is also ac ommonly employed strategy that suits certain synthetic applications.M ethods include hydrogenation of the alkene bond in the adducts (92), [64,132] or alkene epoxidation/dihydroxylation (93). [133,134] In addition, synthetic manipulation of the oxanorbornene exocyclic groups is another means to tune the cycloreversion rate (Scheme 14). [135] This can be conveniently done for instance via redox transformations,f or example by reduction of the anhydride functionality in the adduct 89 and functionalization to 94 a-c as shown in the example in Scheme 14.…”

“…Kinetically blocking the reverse DA process is also a commonly employed strategy that suits certain synthetic applications. Methods include hydrogenation of the alkene bond in the adducts ( 92 ), [64, 132] or alkene epoxidation/dihydroxylation ( 93 ) [133, 134] . In addition, synthetic manipulation of the oxanorbornene exocyclic groups is another means to tune the cycloreversion rate (Scheme 14).…”