Molecular-Level Investigation of Cycloaliphatic Epoxidised Ionic Liquids as a New Generation of Monomers for Versatile Poly(Ionic Liquids)

Demir, Barış; Perli, Gabriel; Chan, Kit‐Ying; Duchet‐Rumeau, Jannick; Livi, Sébastien

doi:10.3390/polym13091512

Cited by 10 publications

(8 citation statements)

References 48 publications

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“…The initial cubic samples were generated at low density (200 Å in each principal direction) to avoid atomic overlaps during the packing of the ions/molecules. The simulation procedure reported in the literature was followed to polymerize the liquid precursor mixtures and predict the thermomechanical properties of the resulting polymers . More information about the simulation methodology has been provided in the Supporting Information.…”

Section: Methodsmentioning

confidence: 99%

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From the Design of Novel Tri- and Tetra-Epoxidized Ionic Liquid Monomers to the End-of-Life of Multifunctional Degradable Epoxy Thermosets

Perli

Wylie

Demir

et al. 2022

ACS Sustainable Chem. Eng.

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The design and development of multifunctional epoxy thermosets have recently stimulated continuous research on new degradable epoxy monomers. Herein, tri-and tetra-epoxidized imidazolium monomers were rationally designed with cleavable ester groups and synthesized on a multigram scale (up to 100 g), yielding room-temperature ionic liquids. These monomers were used as molecular building blocks and cured with three primary amine hardeners having different reactivities, leading to six different network architectures. Overall, the resulting epoxy−amine networks exhibit high thermal stability (>350 °C), excellent mechanical properties combined with a shape memory behavior, glass transition temperatures (T g s) from 55 to 120 °C, and complete degradability under mild conditions. In addition, nonpolarizable, all-atom molecular dynamics simulations were applied in order to investigate the molecular interactions during the polyaddition reaction-based polymerization and then to predict the thermomechanical and mechanical properties of the resulting networks. Thus, this work employs computational chemistry, organic synthesis, and material science to develop high-performance as well as environmentally friendly networks to meet the requirements of the circular economy.

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Section: Methodsmentioning

confidence: 99%

“…The simulation procedure reported in the literature was followed to polymerize the liquid precursor mixtures and predict the thermomechanical properties of the resulting polymers. 63 More information about the simulation methodology has been provided in the Supporting Information.…”

Section: ■ Introductionmentioning

confidence: 99%

From the Design of Novel Tri- and Tetra-Epoxidized Ionic Liquid Monomers to the End-of-Life of Multifunctional Degradable Epoxy Thermosets

Perli

Wylie

Demir

et al. 2022

ACS Sustainable Chem. Eng.

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“…This, in turn, requires custom syntheses for most PILs. Livi and co-workers simulated the properties of homopolymerized epoxy PILs based on the monomer structure to reduce the amount of different syntheses required [96]. In the present work, the versatility and considerable potential of epoxy-functional ILs is further demonstrated via the selection and implementation of different hardeners, resulting in an effective tailoring of the properties of the prepared epoxy-IL networks.…”

Section: [79]mentioning

confidence: 88%

Cross-Linking and Evaluation of the Thermo-Mechanical Behavior of Epoxy Based Poly(ionic Liquid) Thermosets

et al. 2021

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Poly(ionic liquids) (PILs) and ionenes are polymers containing ionic groups in their repeating units. The unique properties of these polymers render them as interesting candidates for a variety of applications, such as gas separation membranes and polyelectrolytes. Due to the vast number of possible structures, numerous synthesis protocols to produce monomers with different functional groups for task-specific PILs are reported in literature. A difunctional epoxy-IL resin was synthesized and cured with multifunctional amine and anhydride hardeners and the thermal and thermomechanical properties of the networks were assessed via differential scanning calorimetry and dynamic mechanical analysis. By the selection of suitable hardeners, the glass transition onset temperature (Tg,onset) of the resulting networks was varied between 18 °C and 99 °C. Copolymerization of epoxy-IL with diglycidyl ether of bisphenol A (DGEBA) led to a further increase of the Tg,onset. The results demonstrate the potential of epoxy chemistry for tailorable PIL networks, where the hardener takes the place of the ligands without requiring an additional synthesis step and can be chosen from a broad range of commercially available compounds.

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“…Dzienia et al, demonstrated the cure kinetics of DGEBA using imidazolium-based ionic liquid curing agents, in which the presence of the salicylate anion results in a highly cross-linked polymerization compared to chloride anion [ 38 ]. Radchenko et al, reported the synthesis of PIL networks based on cycloaliphatic epoxidized ionic liquids with thermomechanical and potential shape memory behaviors [ 39 , 40 ].…”

Section: Introductionmentioning

confidence: 99%

A Computer Simulation Study of Thermal and Mechanical Properties of Poly(Ionic Liquid)s

Shim

Kim

2022

Membranes

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Thermal and mechanical properties of poly(ionic liquid)s (PILs), an epoxidized ionic liquid-amine network, are studied via molecular dynamics simulations. The poly(ionic liquid)s are designed with two different ionic liquid monomers, 3-[2-(Oxiran-2-yl)ethyl]-1-{4-[(2-oxiran-2-yl)ethoxy]phenyl}imidazolium (EIM2) and 1-{4-[2-(Oxiran-2-yl)ethyl]phenyl}-3-{4-[2-(oxiran-2-yl)ethoxy]benzyl}imidazolium (EIM1), each of which is networked with tris(2-aminoethyl)amine, paired with different anions, bis(trifluoromethanesulfonyl)imide (TFSI−) and chloride (Cl−). We investigate how ionic liquid monomers with high ionic strength affect structures of the cross-linked polymer networks and their thermomechanical properties such as glass transition temperature (Tg) and elastic moduli, varying the degree of cross-linking. Strong electrostatic interactions between the cationic polymer backbone and anions build up their strong structures of which the strength depends on their molecular structures and anion size. As the anion size decreases from TFSI− to Cl−, both Tg and elastic moduli of the PIL increase due to stronger electrostatic interactions present between their ionic moieties, making it favorable for the PIL to organize with stronger bindings. Compared to the EIM2 monomer, the EIM1 monomers and TFSI− ions generate a PIL with higher Tg and elastic moduli. This attributes to the less flexible structure of the EIM1 monomer for the chain rotation, in which steric hindrance by ring moieties in the EIM1-based PIL enhances their structural rigidity. The π-π stacking structures between the rings are found to increase in EIM1-based PIL compared to the EIM2-based one, which becomes stronger with smaller Cl− ion rather than TFSI−. The effect of the degree of the cross-linking on thermal and mechanical properties is also examined. As the degree of cross-linking decreases from 100% to 60%, Tg also decreases by a factor of 10–20%, where the difference among the given PILs becomes decreased with a lower degree of cross-linking. Both the Young’s (E) and shear (G) moduli of all the PILs decrease with degree of cross-linking, which the reduction is more significant for the PIL generated with EIM2 monomers. Transport properties of anions in PILs are also studied. Anions are almost immobilized globally with very small structural fluctuations, in which Cl− presents lower diffusivity by a factor of ~2 compared to TFSI− due to their stronger binding to the cationic polymer backbone.

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Molecular-Level Investigation of Cycloaliphatic Epoxidised Ionic Liquids as a New Generation of Monomers for Versatile Poly(Ionic Liquids)

Cited by 10 publications

References 48 publications

From the Design of Novel Tri- and Tetra-Epoxidized Ionic Liquid Monomers to the End-of-Life of Multifunctional Degradable Epoxy Thermosets

From the Design of Novel Tri- and Tetra-Epoxidized Ionic Liquid Monomers to the End-of-Life of Multifunctional Degradable Epoxy Thermosets

Cross-Linking and Evaluation of the Thermo-Mechanical Behavior of Epoxy Based Poly(ionic Liquid) Thermosets

A Computer Simulation Study of Thermal and Mechanical Properties of Poly(Ionic Liquid)s

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