Acid-triggered, degradable and high strength-toughness copolyesters: Comprehensive experimental and theoretical study

Tian, Ying; Li, Jiayi; Hu, Han; Chen, Chao; Li, Fenglong; Ying, Wu; Zheng, Linjie; Zhao, Yi‐Lei; Wang, Jinggang; Zhang, Ruoyu; Zhu, Jin

doi:10.1016/j.jhazmat.2022.128392

Cited by 20 publications

(13 citation statements)

References 60 publications

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“…In our previous work, itaconate-based polyesters could be functionalized through the aza-Michael addition of primary amines, followed by a lactamization step to polyester chain scission . The degradation process is usually chemically regulated, such as hydrolysis under enzymatic, acidic, basic, or neutral conditions, or through acid-degraded spiroacetal units. , Moreover, physical techniques, involving ultrasound fragmentation, − heat treatment, mechanophore installation, as well as through exposure to electromagnetic radiations, , can help control polymer degradation in a more convenient way. Among these physical methods, temperature control is stable and easy to control.…”

Section: Introductionmentioning

confidence: 99%

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

Luan

Jiang³

et al. 2023

Macromolecules

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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.

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Section: Introductionmentioning

confidence: 99%

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

Luan

Jiang³

et al. 2023

Macromolecules

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“…The diffraction peaks of PBAI10 and PBAI30 at 2θ = 21.7° (110) and 22.3° (110) can be attributed to the α-form of the PBA crystal . Moreover, the crystal structures of PBFI30 (17.9, 22.3, 24.7°) and PBTI30 (15.9, 17.3, 20.5, 23.3, 25.1°) were similar to those of PBF , and PBT homopolyesters. These results indicate that the incorporation of itaconic acid units at low contents (no more than 40%) will not affect the crystal structures of the homopolyesters.…”

Section: Resultsmentioning

confidence: 77%

Efficient Synthesis of Itaconate Polyesters with Amine-Triggered Rapid Degradation and Outstanding Mechanical Properties: An Experimental and Theoretical Study on Degradation Mechanisms

Wang

et al. 2022

Macromolecules

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A range of degradable polyesters have been developed as sustainable alternatives for commercial plastics; however, limitations of composting facilities and uncontrolled degradation in the environment hindered their viability. In this study, biobased itaconic acid was selected as an active site to control the degradation of polyesters. A series of PBXI copolyesters with M w 's ranging from 4.86 to 8.31 × 10 4 g/mol and high intrinsic viscosities of more than 1.15 dL/g were successfully synthesized without any crosslinking by selecting appropriate reaction conditions, including condensation temperature and vacuum, effective inhibitor, and catalyst. The obtained copolyesters were semicrystalline, and their T m 's could be regulated from 42.5 to 179.5 °C. They exhibited outstanding elastic modulus (120−598 MPa) and tensile strength (17.9−51.4 MPa) among degradable polymers. Degradation experiments demonstrated that the incorporation of itaconate segments could facilitate both the hydrolysis and enzymatic degradation of polyesters. The state-of-the-art computation and analysis via molecular dynamics (MD) simulations of PBXI−CALB complexes elucidated the enzymatic degradation mechanism. Experimental results proved that, at room temperature, the degradation could be stimulated and regulated by amines without a catalyst and the M n 's of lactamization products rapidly decreased to less than 5000 g/mol within 24 h. Moreover, the copolymerized structure of copolyesters and solvent factors could influence the aza-Michael addition between amines and itaconate units. This work provides a strategy to synthesize biodegradable copolymers with the potential to undergo controlled and rapid in vivo degradation with outstanding mechanical properties.

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“…18,19 Biobased polyurethanes and polyesters with acetal units have also been conveniently degraded under acidic conditions, which can facilitate biodegradation or chemical recycling. 11,20,21 In most reported chemical recycling processes, polymers were completely broken into small compounds and monomers that can be further used for polymerizations. 10,22,23 This means a loss of the initial chemical bonding energy in the polymer backbone and an unfavorable longer recycling loop than mechanical recycling (due to the additional depolymerization− repolymerization process).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Furthermore, spirocyclic acetal structures are sensitive to acidic conditions, which can be utilized to design polymers with degradability or chemical recyclability. For instance, a spiroacetal epoxy monomer has been used to produce cellulose nanofiber composites with chemical recyclability. , Polymers with acetal structures have also been used as drug delivery systems with controlled release. , Biobased polyurethanes and polyesters with acetal units have also been conveniently degraded under acidic conditions, which can facilitate biodegradation or chemical recycling. ,, …”

Section: Introductionmentioning

confidence: 99%

Short-Loop Chemical Recycling via Telechelic Polymers for Biobased Polyesters with Spiroacetal Units

Mankar

Wahlberg

Warlin

et al. 2023

ACS Sustainable Chem. Eng.

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Spirocyclic acetal structures have recently received growing attention in polymer science due to their dual potential to raise the glass transition temperature (T g ) and enable chemical recycling of biobased polymers. In the present work, a vanillinbased diol with a spirocyclic acetal structure was incorporated in a series of rigid amorphous polyesters based on neopentyl glycol and dimethyl terephthalate (DMT). Up to 50 mol % of spirocyclic diol (with respect to DMT) could be incorporated in the copolyesters, but a reasonably high molecular weight was only achieved when ≤30 mol % of the spirocyclic diol was used. The presence of the spiroacetal units in the polyesters not only enhanced the T g (up to 103 °C) and thermal stability (T 5 ≥ 300 °C) but also the oxygen barrier of solution-cast films. We found that the acetal units in the copolyesters could be selectively hydrolyzed under acidic conditions while virtually retaining all of the ester bonds in the polymer backbone. After acidic hydrolysis, telechelic polymers exclusively terminated by two aldehyde end groups were obtained. In this work, we have demonstrated that these telechelic polyesters can be conveniently converted back into poly(acetal-ester)s via cycloacetalization reactions with pentaerythritol.

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Acid-triggered, degradable and high strength-toughness copolyesters: Comprehensive experimental and theoretical study

Cited by 20 publications

References 60 publications

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

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

Efficient Synthesis of Itaconate Polyesters with Amine-Triggered Rapid Degradation and Outstanding Mechanical Properties: An Experimental and Theoretical Study on Degradation Mechanisms

Short-Loop Chemical Recycling via Telechelic Polymers for Biobased Polyesters with Spiroacetal Units

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