Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(41), С. 16181 - 16196

Опубликована: Сен. 16, 2019

The classical division of polymeric materials into thermoplastics and thermosets based on covalent network structure often implies that these categories are distinct irreconcilable. Yet, the past two decades have seen extensive development bridge this gap through incorporation dynamic crosslinks, enabling them to behave as both robust networks moldable plastics. Although their potential utility is significant, growth adaptable (CANs) has obscured line between "thermoplastic" "thermoset" erected a conceptual barrier growing number new researchers entering discipline. This Perspective aims outline fundamental theory CANs provide critical assessment current status. We emphasize throughout unique properties emerge from chemistry, particularly highlight role crosslink exchange mechanism (i.e., dissociative or associative exchange) plays in resultant material under processing conditions. Predominant focus will be thermally induced behavior, majority presently employed chemistries rely thermal stimulus, it simple apply bulk materials. Lastly, identify issues address possible solutions for better understanding within field.

Язык: Английский

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Dynamic covalent chemistry in polymer networks: a mechanistic perspective

Polymer Chemistry, Год журнала: 2019, Номер 10(45), С. 6091 - 6108

Опубликована: Янв. 1, 2019

A selection of dynamic chemistries is highlighted, with a focus on the reaction mechanisms molecular network rearrangements, and how mechanistic profiles can be related to mechanical physicochemical properties polymer materials.

Язык: Английский

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Vitrimers: directing chemical reactivity to control material properties

Chemical Science, Год журнала: 2020, Номер 11(19), С. 4855 - 4870

Опубликована: Янв. 1, 2020

In this minireview, we survey recent advances in the development of vitrimer materials. Focus on how to chemically control their material properties is used highlight challenges for boosting potential emerging class polymer

Язык: Английский

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Vitrimers: Associative dynamic covalent adaptive networks in thermoset polymers

Chemical Engineering Journal, Год журнала: 2019, Номер 385, С. 123820 - 123820

Опубликована: Дек. 16, 2019

Язык: Английский

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Vitrimers: Current research trends and their emerging applications

Materials Today, Год журнала: 2021, Номер 51, С. 586 - 625

Опубликована: Июль 29, 2021

Язык: Английский

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Catalyst-Free Vitrimers from Vinyl Polymers

Macromolecules, Год журнала: 2019, Номер 52(5), С. 2105 - 2111

Опубликована: Фев. 20, 2019

Cross-linked networks feature exceptional chemical and mechanical resilience but consequently lack recyclability. Vitrimers have emerged as a class of materials that the robustness thermosets recyclability thermoplastics without compromising network integrity. Most examples vitrimers involved new polymers with exchangeable bonds within their backbones. In pursuit more universal, commercially viable route, we propose method utilizing available inexpensive reagents to prepare from vinyl monomer-derived prepolymers contain cross-linkable β-ketoester functional groups. Controlled radical copolymerization methyl methracrylate (2-acetoacetoxy)ethyl methacrylate afforded linear were converted into in single step by treatment trifunctional amine. These displayed characteristic features reprocessability over many six (re)processing cycles. Critically, prepared through this process largely retain thermal properties counterparts, suggesting holds significant utility user-friendly relevant approach rational design diverse properties.

Язык: Английский

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Internal Catalysis in Covalent Adaptable Networks: Phthalate Monoester Transesterification As a Versatile Dynamic Cross-Linking Chemistry

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(38), С. 15277 - 15287

Опубликована: Авг. 30, 2019

Covalent adaptable networks (CANs) often make use of highly active external catalysts to provide swift exchange the dynamic chemical bonds. Alternatively, milder species can act as internal when covalently attached matrix and in close proximity In this context, we introduce phthalate monoesters a novel chemistry platform for covalent networks. A low-molecular-weight (MW) model study shows that these undergo fast transesterification via dissociative mechanism, caused by catalysis free carboxylic acid, which reversibly forms an activated phthalic anhydride intermediate. Using chemistry, wide series CANs with broad range properties have been prepared simply curing mixture diols triols bifunctional anhydrides. The nature was confirmed recycling experiments multiple cycles stress relaxation using rheology. proved be resistant deformation but showed marked temperature response their rheological behavior, related reactions high activation energy (120 kJ/mol). While densely cross-linked hydrolytically stable polyester low soluble fractions obtained, found that, swelling hot solvent, gel-to-sol transition happened, resulted full dissolution network.

Язык: Английский

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A fully bio-based polyimine vitrimer derived from fructose

Green Chemistry, Год журнала: 2019, Номер 21(7), С. 1596 - 1601

Опубликована: Янв. 1, 2019

A bio-based polyimine vitrimer containing 100% renewable carbon content has been synthesised and characterised, based on furan dialdehyde derived from fructose.

Язык: Английский

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Block Copolymer Vitrimers

Journal of the American Chemical Society, Год журнала: 2019, Номер 142(1), С. 283 - 289

Опубликована: Дек. 3, 2019

In this report, we merge block copolymers with vitrimers in an effort to realize the prospect of higher-order, nanoscale control over associative cross-link exchange and flow. We show use controlled polymerization as a vital tool understand fundamental structure–property effects through precise polymer architecture molecular weight. Vitrimers derived from self-assembling exhibit superior resistance macroscopic deformation comparison their analogs generated statistical copolymers. Our results suggest that enhanced creep achieved by chain topology can be used tune viscoelastic properties. The arises microphase-separated structure new class materials differentiates counterparts introduces potential topology-control

Язык: Английский

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Fast processing of highly crosslinked, low-viscosity vitrimers

Materials Horizons, Год журнала: 2019, Номер 7(1), С. 104 - 110

Опубликована: Авг. 23, 2019

This study describes a rational approach to go beyond the current processability limits of vitrimer materials, with demonstration low-viscosity fast processing highly crosslinked permanent networks.

Язык: Английский

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