Polybenzoxazines: a sustainable platform for the design of fast responsive and catalyst-free vitrimers based on trans-esterification exchanges

Adjaoud, Antoine; Trejo-Machin, Acerina; Puchot, Laura; Verge, Pierre

doi:10.1039/d1py00324k

Cited by 51 publications

(52 citation statements)

References 65 publications

(98 reference statements)

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“…36 Recently, Verge et al reported a reversible catalyst-free polybenzoxazine vitrimer based on transesterification exchanges. 37 Expanding the scope of dynamic linkages, thermosetting polyurethanes are widely used in adhesives, foams, and coatings. 38 Traditionally, the dissociative reversion of carbamates typically occurred at high temperatures (>200 C).…”

Section: Introductionmentioning

confidence: 99%

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Catalyst‐free reprocessable crosslinked biobased polybenzoxazine‐polyurethane based on dynamic carbamate chemistry

Wen

Bonnaud

Dubois

et al. 2022

J of Applied Polymer Sci

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The introduction of dynamic covalent chemistry into the field of polymer chemistry has resulted in a new class of network polymer materials named covalent adaptable networks (CANs). These new materials have effectively bridged two antagonistic materials, that is, conventional thermoplastic and thermoset polymers together, thanks to these dynamic exchangeable covalent bonds, making them recyclable. In this work, we report a catalyst-free reprocessable polybenzoxazine-polyurethane thermosetting system with activation of carbamate dynamic bond exchange. The curing characteristics and properties of this biobased polybenzoxazine-polyurethane network have been determined by Fourier transform infra-red (FTIR), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMA). Moreover, the tests of the recyclability of the material were successfully achieved under mild reprocess conditions (130 C, 10 min) thanks to the formation of abundant free phenolic hydroxyl groups. This work provides a promising potential for industrial applications as a new recyclable and reprocessable thermosetting polybenzoxazine material.

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Section: Introductionmentioning

confidence: 99%

“…Such as sulfide linkages 35 or metal–ligand interactions 36 . Recently, Verge et al reported a reversible catalyst‐free polybenzoxazine vitrimer based on trans‐esterification exchanges 37 . Expanding the scope of dynamic linkages, thermosetting polyurethanes are widely used in adhesives, foams, and coatings 38 .…”

Section: Introductionmentioning

confidence: 99%

Catalyst‐free reprocessable crosslinked biobased polybenzoxazine‐polyurethane based on dynamic carbamate chemistry

Wen

Bonnaud

Dubois

et al. 2022

J of Applied Polymer Sci

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“…Benzoxazine resin, as a new class of thermosetting polymer, has gained considerable attention in recent years on account of its brilliant heat resistance, excellent flame retardance, and high hydrophobicity [ 13 , 14 , 15 ]. Recently, various dynamic covalent bonds have been introduced into polybenzoxazine networks to achieve self-healabilty or reprocessability [ 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. However, there have been few reports on introducing boronic ester bonds into benzoxazine resins until now.…”

Section: Introductionmentioning

confidence: 99%

Reprocessable Polybenzoxazine Thermosets with High Tgs and Mechanical Strength Retentions Using Boronic Ester Bonds as Crosslinkages

Wang

Zhang

et al. 2022

Polymers

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In order to obtain reprocessable polybenzoxazine thermosets with high heat resistance and mechanical strength retentions, network structures without irreversible parts were constructed via crosslinking benzoxazine oligomers using boronic ester cross-linkers. Firstly, the benzoxazine monomer containing carbon–carbon double bonds was synthesized via the Mannich reaction. After thermal ring-opening polymerization, the benzoxazine oligomer containing carbon–carbon double bonds (OBZ) was yielded. Through the thiol-ene click reaction of the OBZ and dithiol cross-linker bearing boronic ester bonds, the polybenzoxazine thermosets using boronic ester bonds as crosslinkages (OBZ-BDB) were successfully synthesized. The structures of OBZ and OBZ-BDB were characterized by SEC, 1H NMR, and FT-IR measurements. Reprocessing experiments showed that OBZ-BDB has remarkable reprocessability. The retention rates of the tensile strengths through three generations of reprocessing were 98%, 95%, and 84%, respectively. Meanwhile, OBZ-BDB cross-linked by boronic ester bonds had brilliant thermal properties. The Tg of the original OBZ-BDB was 224 °C. With the increase of the reprocessing generations, the Tgs basically remained unchanged.

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“…10 The second group includes the development of new thermoset materials that are easy to recycle, recure, and degrade. To make a sort of materials, dynamic covalent networks such as Diels-Alder (DA) adducts, [11][12][13] disulfide linkages, [14][15][16] imine linkages, [17][18][19][20] trans-esterification, [21][22][23][24] boronic ester trans-esterification, [25][26][27][28] olefin metathesis, [29][30][31] siloxane equilibration, 32,33 trans-amination of vinylogous urethanes [34][35][36][37] and so forth are incorporated into the cured network. However, typical carbon-carbon bonds, ether bonds, carbon-nitrogen bonds and so forth has stronger bond energy than dynamic covalent bonds.…”

Section: Introductionmentioning

confidence: 99%

Review on intrinsically recyclable flame retardant thermosets enabled through covalent bonds

Rashid

Liu

Wei

2022

J of Applied Polymer Sci

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Developing thermosets with inherent recyclability and flame retardancy is a great importance from the views of fire safety, resource conservation and environmental protection. Owing to their superior mechanical properties, versatility, outstanding adhesion‐ability, durability, thermal, and solvent stability comparable to conventional thermosets while demonstrating end‐of‐life reuse, recyclable thermosetting materials have gained much interest as an attractive class of sustainable thermosets. The chemical structure of thermosets includes dynamic covalent networks that provide durability and reprocessability. However, these recyclable thermosets possess significant flammability, limiting their application in automobiles, railways, aircraft, buildings, and electronic items. Thus, it is urgent to include them with flame retardants. The goal of this review paper is to give a broad understanding of the study by highlighting and discussing recent advances as well as future prospects for inherently recyclable flame retardant thermosets (RFRs). Moreover, synthesis methods have been highlighted to improve the design of internally recyclable fire retardant thermosets. A distinct emphasis will be given on the inherent RFRs in terms of flame retardancy, recycling property, physical properties, and thermal stability. Finally, we will explore the importance and threats that intrinsically recyclable flame retardant thermosets face in the future.

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Polybenzoxazines: a sustainable platform for the design of fast responsive and catalyst-free vitrimers based on trans-esterification exchanges

Abstract: This work explores a new strategy, aiming for the synthesis of catalyst-free vitrimers by taking advantage of the abundant number of tertiary amines covalently bound into a polybenzoxazine network.

Cited by 51 publications

References 65 publications

Catalyst‐free reprocessable crosslinked biobased polybenzoxazine‐polyurethane based on dynamic carbamate chemistry

Catalyst‐free reprocessable crosslinked biobased polybenzoxazine‐polyurethane based on dynamic carbamate chemistry

Reprocessable Polybenzoxazine Thermosets with High Tgs and Mechanical Strength Retentions Using Boronic Ester Bonds as Crosslinkages

Review on intrinsically recyclable flame retardant thermosets enabled through covalent bonds

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