Dynamic Covalent Bond: Modes of Activation of the C—ON Bond in Alkoxyamines

Audran, Gérard; Bagryanskaya, Elena G.; Bikanga, Raphaël; Coote, Michelle L.; Guselnikova, Olga; Hammill, Chelsey L.; Marque, Sylvain R. A.; Mellet, Philippe; Postnikov, Pavel

doi:10.1016/j.progpolymsci.2023.101726

Cited by 6 publications

(1 citation statement)

References 143 publications

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“…Moreover, the dissociation energy of the alkoxyamines can be tuned through the molecular structure design. This concept has been particularly investigated in the field of controlled radical polymerization where it is essential to understand the reactivity of C–ON moieties. , The regulation of the dissociation constant and homolysis temperature of polymeric materials carrying alkoxyamines has been extensively investigated in the literature especially to mediate controlled radical polymerization . Nevertheless, studies using alkoxyamines to tune the reprocessing temperature in PU networks are limited, , and the molecular structures employed are 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-based alkoxyamines, − which exhibit higher dissociation temperatures compared to N - tert -butyl- N -[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide, also referred as SG1-type nitroxide alkoxyamines. , For this reason, we decided to research their dynamic behavior in depth.…”

Section: Introductionmentioning

confidence: 99%

Tuning Reprocessing Temperature of Aliphatic Polyurethane Networks by Alkoxyamine Selection

Elizalde,

Pertici,

Aguirresarobe

et al. 2024

ACS Appl. Polym. Mater.

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Recent studies have shown that the largest employed thermoset family, polyurethanes (PUs), has great potential to be reprocessed due to the dynamic behavior of carbamate linkage. However, it requires high temperatures, especially in the case of aliphatic PUs, which causes side reactions besides the desired exchange reaction. To facilitate the reprocessing of aliphatic PUs, in this work, we have explored the dynamic potential of alkoxyamine bonds in PU networks to facilitate the reprocessing under mild conditions considering their fast recombination ability. Taking advantage of the structural effect of the nitroxide and alkyl radicals on the dissociation energy, two different alkoxyamine-based diols have been designed and synthesized to generate PU networks. Our study shows that replacing 50 mol % of a nondynamic diol chain extender with these dynamic blocks boosts the relaxation times of the networks, enabling reprocessing at temperatures as low as 80 °C.

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Section: Introductionmentioning

confidence: 99%

Tuning Reprocessing Temperature of Aliphatic Polyurethane Networks by Alkoxyamine Selection

Elizalde,

Pertici,

Aguirresarobe

et al. 2024

ACS Appl. Polym. Mater.

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Electrochemically Generated Carbocations in Organic Synthesis

Hawkins,

Chalker,

Coote

et al. 2024

Angewandte Chemie

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Investigating Dynamic Changes in 3D‐Printed Covalent Adaptable Polymer Networks

Jia,

Spiegel,

Diehm

et al. 2024

Macro Materials & Eng

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Abstract3D printing technologies have matured to produce complex structures, still they are often limited to static materials. Introducing alkoxyamine bonds into 3D printed structures offers unprecedented possibilities for post‐synthetic modification through nitroxide exchange reaction and nitroxide‐mediated polymerization. This study provides a comprehensive molecular and macroscopic characterization of 3D‐printed alkoxyamine‐containing dynamic covalent adaptable networks. The study provides new insights into their dynamic structural and mechanical alterations, making them promising candidates for advanced applications ranging from biomedical engineering to flexible electronics.

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Dynamic Covalent Bond: Modes of Activation of the C—ON Bond in Alkoxyamines

Cited by 6 publications

References 143 publications

Tuning Reprocessing Temperature of Aliphatic Polyurethane Networks by Alkoxyamine Selection

Tuning Reprocessing Temperature of Aliphatic Polyurethane Networks by Alkoxyamine Selection

Electrochemically Generated Carbocations in Organic Synthesis

Investigating Dynamic Changes in 3D‐Printed Covalent Adaptable Polymer Networks

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