Highly Self-Healable Polymeric Blend Synthesized Using Polymeric Glue with Outstanding Mechanical Properties

Lee, Seoyun; Hong, Pyong Hwa; Kim, Jinsil; Choi, Kiwon; Moon, Gyeongmin; Kang, Jung-Ha; Lee, Sungkoo; Ahn, Jae Beom; Eom, Wonsik; Ko, Min Jae; Hong, Sung Woo

doi:10.1021/acs.macromol.9b02359

Cited by 28 publications

(37 citation statements)

References 39 publications

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“…It was, however, reported that stronger hydrogen bonds are formed between urethane groups and imide groups than between two urethane groups. 23 Hydrogen-bonding interactions can be studied by means of FTIR spectroscopy since they influence the frequency of N−H stretching vibrations (3450−3200 cm −1 ) and carbonyl stretching vibrations (1772−1692 cm −1 ). Table 4 gives an overview of FTIR bands related to non-hydrogen-bonded ("free") and hydrogen-bonded N−H and CO groups.…”

Section: Uv-polymerization All Prepolymers Of Tablementioning

confidence: 99%

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From Slow to Fast Self-Healing at Ambient Temperature of High-Modulus Reversible Poly(methacrylate) Networks. Single- and Dual-Dynamics and the Effect of Phase Separation

et al. 2021

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Reversible poly(methacrylate) networks are synthesized with tunable thermomechanical and self-healing properties. The focus is on highmodulus networks (guide value of around 500 MPa at 25 °C) in combination with fast self-healing for applications as coatings at ambient temperature. In case of a broad temperature window for outdoor applications, mechanical robustness up to 120 °C is aimed for. Methacrylate-functionalized Diels− Alder prepolymers containing furan−maleimide reversible covalent bonds are first synthesized at 25 °C. The prepolymers act as reversible crosslinkers in the subsequent UV-polymerization at 60 °C. Reaction-induced phase separation is achieved by changing the balance between soft and hard blocks, leading to homogeneous and (partially) phaseseparated, fully reversible poly(methacrylate) networks. The incorporation of urethane bonds introduces hydrogen bonding capacity. For comparison, irreversible poly(methacrylate) networks, that is, without reversible Diels−Alder bonds, are synthesized via UVpolymerization of irreversible methacrylate-functionalized prepolymers. A tunable self-healing behavior is demonstrated. The singledynamic high-modulus poly(methacrylate) networks, purely based on reversible Diels−Alder bonds, show the slowest self-healing, for example, for 7 days under ambient conditions. The dual-dynamic high-modulus poly(methacrylate) networks, based on covalent Diels−Alder bonding and supramolecular hydrogen bonding, show the fastest self-healing, for example, for 10 min under ambient conditions if hydrogen bonding is combined with intrinsic local network mobility in case of a (partially) phase-separated network morphology.

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Section: Uv-polymerization All Prepolymers Of Tablementioning

confidence: 99%

“…At the same time, the imide CO peak and the urethane N−H peak shift to lower frequency due to the new hydrogen-bonding interaction between urethane N−H and imide CO. 23 As this was not a primary goal of this work, no further analytical analysis on H-bonding is undertaken.…”

Section: Uv-polymerization All Prepolymers Of Tablementioning

confidence: 99%

From Slow to Fast Self-Healing at Ambient Temperature of High-Modulus Reversible Poly(methacrylate) Networks. Single- and Dual-Dynamics and the Effect of Phase Separation

et al. 2021

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“…13 In addition, the soft segments can provide chain mobility, which contributes to attachment of the damaged surfaces, and diffusion and entanglement of the molecular chains, 14,15 so polyurethane is widely used for self-healing materials. [16][17][18] Polyurethane can heal through noncovalent bonds such as hydrogen bonding, 19,20 metal-ligand, 21,22 host-guest, 23 π-π stacking 24 ; van der Waals interaction, 25 and interdiffusion, 26 also heal through dynamic covalent bonds such as Diels-Alder reaction, 27,28 disulfide, 29,30 diselenide, 31 ditelluride, 32 imine, 33 hindered urea, 34 or oxime-carbamate. 35 However, the relationship among transparency, self-healing, and structure of polymers needs to be further explored.…”

Section: Introductionmentioning

confidence: 99%

Transparency‐tunable and moderate‐temperature healable thermoplastic polyurethane elastomer based on bisphenol A chain‐extender

Xiang

Chen

Wang

et al. 2020

J of Applied Polymer Sci

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Transparent self-healing polymers have a promising future, but the research on the relationship among transparency, self-healing, and structure is still challenging. The thermoplastic polyurethane elastomers containing aryl carbamate were prepared by the reaction of isocyanate-terminated prepolymer and chain-extender bisphenol A (BPA). On the one hand, the thermoplastic polyurethane elastomer could heal at a relatively low temperature due to the exchange of aryl carbamate, and exhibits 83% of healing efficiency at 90 C for 2 h. On the other hand, two methyl groups of BPA hinder the crystallization of hard segments in polyurethane, so the domain of hard segments is amorphous, while the microcrystals of soft segments dispersed in the polyurethane are affected by the content of hard segments, therefore, the transparency of polyurethane can be tailored by the content of hard segments. It provides a simple design and a feasible preparation method for transparent self-healing polymer.

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“…Figure 4 and Table 3 show the chemical structures of U, T, and E and the designations and compositions of the samples used for the model system. Based on previous reports [22], it is known that urethane forms three different types of hydrogen bonds (free (noN-Hydrogen bonded), single-hydrogen bonds, and double-hydrogen bonds) [21,23]. As shown in Figure 5a, the FT-IR spectrum of U100 (pure U) showed the double-hydrogen bonded C=O band at 1690.3 cm −1 , the single-hydrogen bonded C=O band (about 1715.0 cm −1 ) as a shoulder, and the free C=O band (about 1740.6 cm −1 ) as a weak shoulder (barely detectable).…”

Section: Optical Propertiesmentioning

confidence: 99%

A Heterocyclic Polyurethane with Enhanced Self-Healing Efficiency and Outstanding Recovery of Mechanical Properties

et al. 2020

Self Cite

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A functional polyurethane based on the heterocyclic group was synthesized and its self-healing and mechanical properties were examined. To synthesize a heterocyclic polyurethane, a polyol and a heterocyclic compound with di-hydroxyl groups at both ends were blended and the blended solution was reacted with a crosslinker containing multiple isocyanate groups. The heterocyclic polyurethane demonstrates better self-healing efficiency than the conventional polyurethane with no heterocyclic groups. Furthermore, unlike the conventional self-healing materials, the heterocyclic polyurethane examined in this study shows an outstanding recovery of the mechanical properties after the self-healing process. These results are attributed to the unique supramolecular network resulting from the strong hydrogen bonding interaction between the urethane group and the heterocyclic group in the heterocyclic polyurethane matrix.Polymers 2020, 12, 968 2 of 11 several decades [7]. While they are more susceptible to damage caused by mechanical stress because of their low mechanical surface properties, these materials can effectively self-heal the areas damaged by the mechanical stress. In light of the critical issues mentioned above, self-healable polymeric coating materials will be preferred to hard coating materials for application in flexible displays. Therefore, endowing conventional polymeric materials with the ability to self-heal both dents and scratches is considered to be vital for the development of next-generation flexible displays [8,9].Traditionally, both extrinsic and intrinsic strategies have been employed to introduce the self-healing capability to polymeric materials. Extrinsic systems depend on embedded capsules or vascular networks [10][11][12]. When the material is damaged, the embedded container will release the contained healing agents to heal the damage by polymerization or chemical reaction. However, repeated healing at the same site is inherently difficult due to the limited amount of the healing agent inside the container, and the healing ability will disappear immediately after the healing agent is depleted [7]. By contrast, intrinsic systems utilize the reversible interaction between the components of the matrix [13][14][15][16], allowing them to repeatedly self-heal the same damaged areas. It is also noted that in contrast to intrinsic systems, it is difficult for the extrinsic systems to maintain the initial optical properties after the self-healing process because of the large difference in the color and refractive index between the intact matrix and the healed region. For these reasons, it is concluded that intrinsic systems are a more appropriate solution for applications, such as in display technologies, that require excellent optical properties.Polyurethane is a widely used intrinsic self-healing material that has been extensively studied because it can effectively recover from the dents on the surface due to its high elasticity [17][18][19][20][21]. However, while polyurethane can self-heal the dents on...

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Highly Self-Healable Polymeric Blend Synthesized Using Polymeric Glue with Outstanding Mechanical Properties

Cited by 28 publications

References 39 publications

From Slow to Fast Self-Healing at Ambient Temperature of High-Modulus Reversible Poly(methacrylate) Networks. Single- and Dual-Dynamics and the Effect of Phase Separation

From Slow to Fast Self-Healing at Ambient Temperature of High-Modulus Reversible Poly(methacrylate) Networks. Single- and Dual-Dynamics and the Effect of Phase Separation

Transparency‐tunable and moderate‐temperature healable thermoplastic polyurethane elastomer based on bisphenol A chain‐extender

A Heterocyclic Polyurethane with Enhanced Self-Healing Efficiency and Outstanding Recovery of Mechanical Properties

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