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The influence of stereochemistry on the reactivity of the Diels-Alder cycloaddition and the implications for reversible network polymerization. / Cuvellier, Audrey; Verhelle, Robrecht René; Brancart, Joost; Vanderborght, Bram; Van Assche, Guy; Rahier, Hubert.

2018. Poster session presented at 12th European Symposium on Thermal Analysis and Calorimetry, Brasov, Romania.

Research output: Unpublished contribution to conferencePosterResearch

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@conference{b7729420b8bb4708b049c06e8db14440,
title = "The influence of stereochemistry on the reactivity of the Diels-Alder cycloaddition and the implications for reversible network polymerization",
abstract = "The Diels-Alder reaction is one of the most studied thermoreversible equilibrium reactions. At low temperatures, the Diels-Alder cycloadduct is formed predominantly, whereas at higher temperatures the equilibrium shifts towards the reactants, which are in this study a furan and a maleimide. Their fast reaction kinetics and high conversion make them suitable candidates for self-healing networks, which can be healed at elevated temperatures due to the thermo-reversible crosslinking. In previous work, these materials have been employed in self-healing coatings [1] and self-healing soft robotic actuators [2]. In the current work, the reaction kinetics of the Diels-Alder reaction between furan and maleimide is thoroughly investigated in view of these applications.Two stereoisomeric cycloadducts can be formed depending on the suprafacial approach between the furan and maleimide functional groups. The exo isomer (bulkier sides of the diene and dieneophile lie away from each other) is the more thermodynamically stable adduct since less steric hindrance is occurring. The endo isomer (bulkier sides lie above each other) forms faster due to a lower activation energy barrier. Although the stereochemistry is well known, its effect on the reactivity, thermal reversibility, and kinetics is often overlooked in literature. The few kinetics studies determining individual kinetics parameters for both isomers were performed in a solvent, affecting the reaction kinetics. In this study, an amorphous, liquid bismaleimide is used, allowing a detailed calorimetric analysis of the Diels-Alder reaction kinetics between furan and maleimide, without the interference of a solvent in the reaction kinetics. For the kinetic modelling, an in-house developed Matlab software was used, which permits optimizing rate constants and activation energies to fit the isothermal (microcalorimetry) and non-isothermal (DSC) data. The kinetic model has been verified using time-resolved and temperature-controlled 1H NMR spectroscopy.[1] J. Brancart, G. Scheltjens, T. Muselle, B. Van Mele, H. Terryn, G. Van Assche, J. Intell. Mater. Syst. Struct. 25 (2014) 40–46[2] S. Terryn, J. Brancart, D. Lefeber, G. Van Assche, B. Vanderborght, IEEE Robot. Autom. Lett. 3 (2017) 16–21",
author = "Audrey Cuvellier and Verhelle, {Robrecht Ren{\'e}} and Joost Brancart and Bram Vanderborght and {Van Assche}, Guy and Hubert Rahier",
year = "2018",
month = "8",
day = "25",
language = "English",
note = "12th European Symposium on Thermal Analysis and Calorimetry, ESTAC 12 ; Conference date: 27-08-2018 Through 30-08-2018",

}

RIS

TY - CONF

T1 - The influence of stereochemistry on the reactivity of the Diels-Alder cycloaddition and the implications for reversible network polymerization

AU - Cuvellier, Audrey

AU - Verhelle, Robrecht René

AU - Brancart, Joost

AU - Vanderborght, Bram

AU - Van Assche, Guy

AU - Rahier, Hubert

PY - 2018/8/25

Y1 - 2018/8/25

N2 - The Diels-Alder reaction is one of the most studied thermoreversible equilibrium reactions. At low temperatures, the Diels-Alder cycloadduct is formed predominantly, whereas at higher temperatures the equilibrium shifts towards the reactants, which are in this study a furan and a maleimide. Their fast reaction kinetics and high conversion make them suitable candidates for self-healing networks, which can be healed at elevated temperatures due to the thermo-reversible crosslinking. In previous work, these materials have been employed in self-healing coatings [1] and self-healing soft robotic actuators [2]. In the current work, the reaction kinetics of the Diels-Alder reaction between furan and maleimide is thoroughly investigated in view of these applications.Two stereoisomeric cycloadducts can be formed depending on the suprafacial approach between the furan and maleimide functional groups. The exo isomer (bulkier sides of the diene and dieneophile lie away from each other) is the more thermodynamically stable adduct since less steric hindrance is occurring. The endo isomer (bulkier sides lie above each other) forms faster due to a lower activation energy barrier. Although the stereochemistry is well known, its effect on the reactivity, thermal reversibility, and kinetics is often overlooked in literature. The few kinetics studies determining individual kinetics parameters for both isomers were performed in a solvent, affecting the reaction kinetics. In this study, an amorphous, liquid bismaleimide is used, allowing a detailed calorimetric analysis of the Diels-Alder reaction kinetics between furan and maleimide, without the interference of a solvent in the reaction kinetics. For the kinetic modelling, an in-house developed Matlab software was used, which permits optimizing rate constants and activation energies to fit the isothermal (microcalorimetry) and non-isothermal (DSC) data. The kinetic model has been verified using time-resolved and temperature-controlled 1H NMR spectroscopy.[1] J. Brancart, G. Scheltjens, T. Muselle, B. Van Mele, H. Terryn, G. Van Assche, J. Intell. Mater. Syst. Struct. 25 (2014) 40–46[2] S. Terryn, J. Brancart, D. Lefeber, G. Van Assche, B. Vanderborght, IEEE Robot. Autom. Lett. 3 (2017) 16–21

AB - The Diels-Alder reaction is one of the most studied thermoreversible equilibrium reactions. At low temperatures, the Diels-Alder cycloadduct is formed predominantly, whereas at higher temperatures the equilibrium shifts towards the reactants, which are in this study a furan and a maleimide. Their fast reaction kinetics and high conversion make them suitable candidates for self-healing networks, which can be healed at elevated temperatures due to the thermo-reversible crosslinking. In previous work, these materials have been employed in self-healing coatings [1] and self-healing soft robotic actuators [2]. In the current work, the reaction kinetics of the Diels-Alder reaction between furan and maleimide is thoroughly investigated in view of these applications.Two stereoisomeric cycloadducts can be formed depending on the suprafacial approach between the furan and maleimide functional groups. The exo isomer (bulkier sides of the diene and dieneophile lie away from each other) is the more thermodynamically stable adduct since less steric hindrance is occurring. The endo isomer (bulkier sides lie above each other) forms faster due to a lower activation energy barrier. Although the stereochemistry is well known, its effect on the reactivity, thermal reversibility, and kinetics is often overlooked in literature. The few kinetics studies determining individual kinetics parameters for both isomers were performed in a solvent, affecting the reaction kinetics. In this study, an amorphous, liquid bismaleimide is used, allowing a detailed calorimetric analysis of the Diels-Alder reaction kinetics between furan and maleimide, without the interference of a solvent in the reaction kinetics. For the kinetic modelling, an in-house developed Matlab software was used, which permits optimizing rate constants and activation energies to fit the isothermal (microcalorimetry) and non-isothermal (DSC) data. The kinetic model has been verified using time-resolved and temperature-controlled 1H NMR spectroscopy.[1] J. Brancart, G. Scheltjens, T. Muselle, B. Van Mele, H. Terryn, G. Van Assche, J. Intell. Mater. Syst. Struct. 25 (2014) 40–46[2] S. Terryn, J. Brancart, D. Lefeber, G. Van Assche, B. Vanderborght, IEEE Robot. Autom. Lett. 3 (2017) 16–21

M3 - Poster

ER -

ID: 39421538