Tunable Thermal-Induced Degradation in Fully Bio-Based Copolyesters with Enhanced Mechanical and Water Barrier Properties

Abstract

Bio-based fumaric acid act as a key monomer for the fabrication of high-performance and thermal-induced degradation polymers. Obtained poly(butylene 2,5-furandicarboxylate/ fumarate) copolyesters had a high number-average molecular weight from 27,500 to 37,600 g/mol. Trans C�C bonds and the conjugated effect provide interesting properties. Influenced by the thermal history, the elastic modulus and tensile strength (>50 MPa) are much higher than PBAT. Trans C�C bonds of fumaric acid and intermolecular interactions of furan rings restrict the diffusion of gas and water molecules. Specifically, the water barrier is 4−12 times better than PBAT, filling the gap in biodegradable food packaging. The hydrolysis resistance of fumarate segments provides good durability during their life span. The functionalization of PBFFu by thiol-Michael addition was performed at room temperature. Three substituent groups bring different conditions of pendant amino groups, resulting in the thermal-induced intramolecular cyclization from 40 to 100 °C. Fumaric acid could be a critical point to achieve the coordination of high-performance and temperature-induced degradation.

Synthesis of Biobased Poly(butylene Furandicarboxylate) Containing Polysulfone with Excellent Thermal Resistance Properties

“…Throughout the content range, distinct diffraction peaks are observable in the XRD patterns of the copolyesters. The crystalline structure of PBF, reported previously, featured diffraction peaks at 18.6, 23.3, and 25.6° corresponding to the (001), (010), and (100) planes, respectively. ,, PBFES5 and PBFES30 exhibit diffraction peaks akin to pure PBF, signifying the presence of PBF crystals. However, with an increasing content of the HEPES oligomer, the diffraction intensity of PBF crystals gradually diminishes and the spherical crystals weaken.…”

Fully Bio‐Based 2,5‐Furandicarboxylic Acid Polyester toward Plastics with Mechanically Robust, Excellent Gas Barrier and Fast Degradation

“…Current linear monomer-modified PBF copolymers were summarized in Figure 3 (f) by defining the rate of hydrolysis (wt %/day) as the ratio of weight loss to hydrolysis days. Although the introduction of adipic acid, [25l] diglycolic acid, [26] ɛ-caprolactone, [27] lactic acid, [25m] succinic acid, [26a,28] fumaric acid, [29] glycolic acid, [9] and DMC [24] into the backbone structure successfully imparted hydrolysis to PBF, the hydrolysis rates did not reach 1 wt%/day. It was worth noting that when the addition amount was less than 20 %, all copolyesters except lactic acid remained non degradable polyester, while PBO 20 F exhibited a hydrolysis rate of 0.26 wt%/day.…”

Modification of Biodegradable Poly(butylene carbonate) with Succinic Acid: High Thermal and Barrier Properties

“…This is a common phenomenon in copolyesters. 18,36 Additionally, the ΔH m ′ of PBCS28 being only 0.2 J/g indicates its extremely poor crystallization ability. The relationships between T m1 ′, T m2 ′, ΔH m ′, and the BS molar fraction are clearly depicted in Figure 3d,e.…”