Elastic vitrimers: Beyond thermoplastic and thermoset elastomers

Luo, Jiancheng; Demchuk, Zoriana; Zhao, Xiao; Saito, Tomonori; Tian, Ming; Sokolov, Alexei P.; Cao, Pengfei

doi:10.1016/j.matt.2022.04.007

Cited by 148 publications

(121 citation statements)

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“…Furthermore, it has been reported that inclusion of dithioacetal bonds and their derivatives into crosslinked polymer networks leads to the successful developments of vitrimers. [53][54][55][56][57] Vitrimer is a class of reprocessible thermosetting polymers that can undergo topological rearrangements by thermally activated exchange reactions. [58][59][60][61][62][63][64][65][66][67] We demonstrate here that crosslinked PDTA with a high amount of dithioacetal bonds behaves as a vitrimer at elevated temperatures in the bulk state without any depolymerization.…”

Section: Introductionmentioning

confidence: 99%

Dithioacetal Polymers Capable of Chemical Recycling to Macrocyclic Monomers and Formation of Vitrimers

Kariyawasam

Rolsma

Yang

2022

Preprint

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Polymers capable of chemical recycling to monomers are highly desirable to produce sustainable materials with a circular economy. We here report a highly efficient ring-chain recycling of polydithioacetal (PDTA) via ring-closing depolymerization (RCD) and entropy-driven ring-opening polymerization (ED-ROP). Pristine PDTAs can be conveniently synthesized via a one-step reaction using 3,4,5-trimethoxybenzaldehyde and α,ω-alkyl dithiols with an acid catalyst. The resulting PDTAs undergo acid-catalyzed RCD with refluxing toluene to yield a mixture of macrocycles of various sizes with conversions of 75-95%. ED-ROP of these macrocyclic monomer mixtures in solution at room temperature affords virgin PDTAs, reaching high conversions of 80-95% within 2 h. Owing to the stability of dithioacetals, PDTAs are far more stable than the acetal counterparts, resisting hydrolysis under both acidic and basic conditions. With a floor temperature below 0 °C, depolymerization is not a concern in the bulk state even in the presence of residual catalysts as polymerization is favored at higher temperatures for ED-ROP. Once crosslinked, the network behaves as a vitrimer enabled by temperature-activated interchain exchange of dithioacetals in the bulk state. The vitrimer depolymerizes into macrocyclic monomers in solvent which can repolymerize to regenerate the vitrimer.

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Section: Introductionmentioning

confidence: 99%

Dithioacetal Polymers Capable of Chemical Recycling to Macrocyclic Monomers and Formation of Vitrimers

Kariyawasam

Rolsma

Yang

2022

Preprint

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“…Therefore, the structure of characteristic associative intermediates of vitrimers and the corresponding reaction kinetics are not well understood, even though mentioned in the literature. [6][7][8]46 Because of the deficient knowledge of the associative effect on dynamics, the dynamic behaviors of vitrimers are usually evaluated superficially through experiments such as stress relaxation and reprocessing. 12,21,27,47,48 In this work, we developed a theoretical model to describe the structure and dynamics of associative exchange dynamic polymer networks considering both associative and dissociative states.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, covalent adaptable networks (CANs) have emerged as an elegant structure design strategy to engineer functional polymers that combine the advantageous properties of conventional thermoplastics and thermosets. − According to different bond exchange reaction mechanisms, CANs could be divided into two classes: either “dissociative” CANs whose crosslinks are cleaved into their individual constituted reactive partners before regenerating, or “associative” CANs with existing fixed crosslinks in the form of associative intermediates. − Vitrimer is a typical example of “associative” CANs, first proposed by the Leibler group based on the classical transesterification in epoxy networks. , Subsequently, many dynamic crosslinking chemistries are utilized to construct novel vitrimers, including dioxaborolane metathesis, , vinylogous urethanes, , olefin metathesis, , diketoenamine exchange, disulfides, siloxane equilibration, phosphate triester transesterification, hemiaminals, trans-carbonation exchange, and so on. While new types of reversible covalent bonds are successively developed, more attention is attracted to further explore the exchange mechanism and dynamics of CANs, especially for vitrimers.…”

Section: Introductionmentioning

confidence: 99%

“…In these works, the associative exchange reaction was indeed treated as a dissociative exchange reaction. Therefore, the structure of characteristic associative intermediates of vitrimers and the corresponding reaction kinetics are not well understood, even though mentioned in the literature. − , Because of the deficient knowledge of the associative effect on dynamics, the dynamic behaviors of vitrimers are usually evaluated superficially through experiments such as stress relaxation and reprocessing. ,,,, …”

Section: Introductionmentioning

confidence: 99%

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Structure and Dynamics of Associative Exchange Dynamic Polymer Networks

Cheng

Zhao

et al. 2022

Macromolecules

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Introducing dynamic covalent bonds can breathe life into polymers by endowing recyclability and tunability to materials, but the characteristic structure and dynamics of associative exchange dynamic polymer networks are yet to be understood. In this study, we present a model to analyze the structure of associative intermediates and the kinetic process of associative exchange. The relationship between the reaction equilibrium constant and the plateau modulus of the associative exchange dynamic polymer networks is established. The model was validated by vinylogous urethane model vitrimers (BPOVU) with different stoichiometric ratios at various temperatures in the equilibrium state. Meanwhile, the thermodynamics and kinetics of BPOVU vitrimers were further analyzed. The model could provide a fundamental understanding of the associative exchange reaction and help direct promising emerging polymer designs and applications.

show abstract

“…Furthermore, inclusion of dithioacetal bond and its derivatives into crosslinked polymer networks have led to the successful developments of vitrimers. [53][54][55][56][57] Vitrimer is a class of reprocessible thermosetting polymers that can undergo topological rearrangements by thermally activated exchange reactions. [58][59][60][61][62][63][64][65][66][67] We demonstrate that crosslinked PDTA with a high amount of dithioacetal bonds behaves as vitrimers at elevated temperatures in the bulk state without any depolymerization.…”

Section: Introductionmentioning

confidence: 99%

Dithioacetal Polymers Capable of Chemical Recycling to Macrocyclic Monomers and Formation of Vitrimers

Kariyawasam

Rolsma

Yang

2022

Preprint

View full text Add to dashboard Cite

Polymers capable of chemical recycling to monomers are highly desirable to produce sustainable materials with a circular economy. We here report a highly efficient ring-chain recycling of linear polydithioacetal (PDTA) via ring-closing depolymerization (RCD) and entropy-driven ring-opening polymerization (ED-ROP). Furthermore, once crosslinked, the network behaves as a vitrimer enabled by temperature-activated interchain exchange of dithioacetals in the bulk state. The vitrimer depolymerizes into macrocyclic monomers in solvent which can repolymerize to regenerate the vitrimer. Pristine linear PDTAs can be conveniently synthesized via a one-step reaction using 3,4,5-trimethoxybenzaldehyde and α,ω-alkyl dithiols with an acid catalyst. The resulting PDTAs undergo acid-catalyzed RCD with refluxing toluene to yield a mixture of macrocycles of various sizes with conversions of 75-95%. ED-ROP of these macrocyclic monomer mixtures in solution at room temperature affords virgin PDTAs, reaching high conversions of 80-95% within 2 h. Owing to the stability of dithioacetals, PDTAs are far more stable than the acetal counterparts, resisting hydrolysis under both acidic and basic conditions. With a floor temperature below 0 °C, depolymerization is not a concern in the bulk state even in the presence of residual catalysts as polymerization is favored at higher temperatures for ED-ROP.

show abstract

Elastic vitrimers: Beyond thermoplastic and thermoset elastomers

Cited by 148 publications

References 148 publications

Dithioacetal Polymers Capable of Chemical Recycling to Macrocyclic Monomers and Formation of Vitrimers

Dithioacetal Polymers Capable of Chemical Recycling to Macrocyclic Monomers and Formation of Vitrimers

Structure and Dynamics of Associative Exchange Dynamic Polymer Networks

Dithioacetal Polymers Capable of Chemical Recycling to Macrocyclic Monomers and Formation of Vitrimers

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