Photopatternable and self-healable ionogels for organic thin-film transistors

Kim, Seungjun; Yeo, Jiyeong; Kim, Su Jung; Park, Soeun; Cho, Kyung Gook; Paeng, Keewook; Lee, Keun Hyung; Kim, Myungwoong

doi:10.1016/j.orgel.2023.106895

Cited by 3 publications

(2 citation statements)

References 52 publications

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“…41,42,48,50,52 To our knowledge, only three studies have employed an aromatic disulfide cross-linker with alkene-containing end groups (acrylate or methacrylate) which could enable free-radical polymerization (FRP). 51,54,55 Two of these simply used their cross-linkers as reagents in a stepgrowth system; 54,55 although the third employed FRP, its focus was the creation of a photoresist rather than a reprocessable CAN. 51 As such, there is substantial opportunity for the examination of an aromatic disulfide cross-linker in the context of reprocessable CAN synthesis under conventional FRP conditions, as this would allow for potential applicability to commercially produced polymer networks.…”

Section: Introductionmentioning

confidence: 99%

“…Aromatic disulfide linkages, in which the sulfur–sulfur bond is flanked by phenyl rings, have seen use in introducing dynamic character to systems such as polyurethane elastomers and epoxy resins. ,,, The reduced BDE of the aromatic disulfide chemistry (typically 190–230 kJ/mol, with some cases as low as 150 kJ/mol) , relative to the general disulfide bond facilitates the [2 + 1] radical-mediated mechanism in the absence of catalysts, thereby allowing for catalyst-free self-healing and reprocessability in systems in which the linkages are incorporated . A range of aromatic disulfide-containing reagents have been used in prior studies, typically involving substitutions to a functional group at the para position of the phenyl rings; bis(4-aminophenyl) disulfide is particularly popular due to the reactions enabled by the amine group it contains, but compounds with alcohol, glycidyl, isocyanate, and other groups have also seen use in various systems. ,, However, given that the majority of these compounds are bis-disulfides and can therefore serve as difunctional monomers, most published systems incorporating aromatic disulfide chemistry involve synthesis via step-growth or condensation polymerization. ,,,, To our knowledge, only three studies have employed an aromatic disulfide cross-linker with alkene-containing end groups (acrylate or methacrylate) which could enable free-radical polymerization (FRP). ,, Two of these simply used their cross-linkers as reagents in a step-growth system; , although the third employed FRP, its focus was the creation of a photoresist rather than a reprocessable CAN . As such, there is substantial opportunity for the examination of an aromatic disulfide cross-linker in the context of reprocessable CAN synthesis under conventional FRP conditions, as this would allow for potential applicability to commercially produced polymer networks.…”

Section: Introductionmentioning

confidence: 99%

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Reprocessable Covalent Adaptable Networks via Free-Radical Polymerization with an Aromatic Disulfide Cross-Linker

Suazo,

Torkelson

2024

ACS Appl. Polym. Mater.

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Aromatic disulfides have seen widespread use in covalent adaptable networks (CANs), though previous studies have exclusively used step-growth methods to integrate them into CANs. Here, we describe a case in which an aromatic disulfidebased cross-linker, bis(4-methacryloyloxyphenyl) disulfide, also called BiPheS methacrylate or BPMA, is incorporated into a CAN by nonstep-growth polymerization. Free-radical copolymerization of n-hexyl methacrylate with 5 mol % BPMA results in a CAN which exhibits full recovery of cross-link density and thermomechanical properties across multiple reprocessing cycles. The CAN rubbery-plateau storage modulus is directly proportional to absolute temperature, characteristic of a constant cross-link density, even at temperatures where the CAN is reprocessable. Indeed, the BPMA-based CAN exhibits a constant cross-link density, and thus associative dynamic character, at temperatures up to at least 200 °C, enabling it to be used in elevated-temperature applications without risk of loss of network character. Under a 3.0 kPa shear stress, the CAN exhibits almost total arrest of creep up to 180 °C and major creep suppression at its reprocessing temperature of 200 °C, overcoming a potential Achilles' heel associated with CANs. Thus, the integration of aromatic disulfides into CANs by free-radical polymerization provides a facile route to produce recyclable networks that maintain network character at very high temperature, contributing to polymer network sustainability. Finally, we determined an Arrhenius apparent activation energy of ∼100 kJ/mol for the CAN stress relaxation and creep viscosity. This value differs substantially from the BPMA bond dissociation energy but agrees with the activation energy for the alpha-relaxation of poly(n-hexyl methacrylate) (PHMA). This indicates that the temperature dependence of these viscoelastic responses in our associative-type CAN is defined by the temperature dependence of the cooperative segmental mobility of PHMA, which makes up 95 mol % of the CAN.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reprocessable Covalent Adaptable Networks via Free-Radical Polymerization with an Aromatic Disulfide Cross-Linker

Suazo,

Torkelson

2024

ACS Appl. Polym. Mater.

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Supramolecular Association of a Block Copolymer via Strong Hydrogen Bonding to Form Self-Healable Ionogels

Kim,

Park,

Kim

et al. 2024

ACS Appl. Mater. Interfaces

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The drive to enhance the operational durability and reliability of stretchable and wearable electronic and electrochemical devices has led to the exploration of self-healing materials that can recover from both physical and functional failures. In the present study, we fabricated a self-healable solid polymer electrolyte, referred to as an ionogel, using reversible hydrogen bonding between the ureidopyrimidone units of a block copolymer (BCP) network swollen in an ionic liquid (IL). The BCP consisted of poly(styrene-b-(methyl acrylate-r-ureidopyrimidone methacrylate)) [poly(S-b-(MA-r-UPyMA)], with the IL-phobic polystyrene forming micellar cores that were interconnected via intercorona hydrogen bonding between the ureidopyrimidone units. By precisely regulating the molecular weight and the composition of the hydrogen-bondable motifs, the mechanical, electrical, and self-healing characteristics of the ionogel were systematically evaluated. The resulting ionogel samples exhibited suitable stretchability, ionic conductivity, and room-temperature self-healability due to reversible hydrogen bonding. To highlight the applicability of the self-healing ionogel as a high-capacitance gate insulator, an electrolyte-gated transistor (EGT) was fabricated using a poly(3-hexylthiophene-2,5-diyl) semiconductor, and the performance of the EGT was fully recovered from a complete cut without any external stimuli.

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Development of functional polymer gel electrolytes and their application in next-generation lithium secondary batteries

Tamate

2024

Polym J

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Photopatternable and self-healable ionogels for organic thin-film transistors

Cited by 3 publications

References 52 publications

Reprocessable Covalent Adaptable Networks via Free-Radical Polymerization with an Aromatic Disulfide Cross-Linker

Reprocessable Covalent Adaptable Networks via Free-Radical Polymerization with an Aromatic Disulfide Cross-Linker

Supramolecular Association of a Block Copolymer via Strong Hydrogen Bonding to Form Self-Healable Ionogels

Development of functional polymer gel electrolytes and their application in next-generation lithium secondary batteries

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