Dynamics of Associative Polymers with High Density of Reversible Bonds

Nian, Shifeng; Patil, Shalin; Zhang, Siteng; Kim, Myoeum; Chen, Quan; Zhernenkov, Mikhail; Ge, Ting; Cheng, Shiwang; Cai, Li‐Heng

doi:10.1103/physrevlett.130.228101

Cited by 10 publications

(23 citation statements)

References 65 publications

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“…B and C are essentially the same except that C carries an amide group. Thus, the size of a Kuhn monomer of the middle block nearly does not change with the fraction λ of reversible groups . Moreover, an amide–amide hydrogen bond has a strength of ϵ b ≈ 20 k B T , which is weak enough to dissociate at laboratory time scales at room temperature yet strong enough for efficient energy dissipation.…”

Section: Resultsmentioning

confidence: 99%

“…Because the two polymers carry high fractions of associative groups that are no less than 0.8 sticker per Kuhn monomer, they can be considered as a homopolymer consisting of renormalized Kuhn monomers. 25 Thus, all polymers follow the same Rouse dynamics, and the only difference is that the basic time scale�the relaxation time of a renormalized Kuhn monomer τ s �increases with λ. Recently, we experimentally showed that at room temperature τ s increases exponentially with the fraction of associative groups: τ s = τ 0 exp(αλ), in which τ 0 is the monomer relaxation time without associative groups and α is a constant equal to 8.6 ± 1.2.…”

Section: Resultsmentioning

confidence: 99%

“…This behavior is attributed to the similar relaxation dynamics of the associative polymers despite different fractions of reversible groups. Because the two polymers carry high fractions of associative groups that are no less than 0.8 sticker per Kuhn monomer, they can be considered as a homopolymer consisting of renormalized Kuhn monomers . Thus, all polymers follow the same Rouse dynamics, and the only difference is that the basic time scalethe relaxation time of a renormalized Kuhn monomer τ s increases with λ.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we developed a new class of associative polymers that carry an unprecedentedly high fraction of stickers that is no less than 0.8 sticker per Kuhn segment. 25 The stickers are amide groups that can form pairwise double hydrogen bonds without microphase separation. This starkly contrasts with the behavior observed in most existing associative polymers, where sticker interactions often result in nanoscale aggregations or even microphase separation.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we developed a new class of associative polymers that carry an unprecedentedly high fraction of stickers that is no less than 0.8 sticker per Kuhn segment . The stickers are amide groups that can form pairwise double hydrogen bonds without microphase separation.…”

Section: Introductionmentioning

confidence: 99%

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3D Printable Modular Soft Elastomers from Physically Cross-linked Homogeneous Associative Polymers

Kim,

Nian,

Rau

et al. 2024

ACS Polym. Au

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printing of elastomers enables the fabrication of many technologically important structures and devices. However, there remains a critical need for the development of reprocessable, solvent-free, soft elastomers that can be printed without the need for post-treatment. Herein, we report modular soft elastomers suitable for direct ink writing (DIW) printing by physically cross-linking associative polymers with a high fraction of reversible bonds. We designed and synthesized linear-associative-linear (LAL) triblock copolymers; the middle block is an associative polymer carrying amide groups that form double hydrogen bonding, and the end blocks aggregate to hard glassy domains that effectively act as physical cross-links. The amide groups do not aggregate to nanoscale clusters and only slow down polymer dynamics without changing the shape of the linear viscoelastic spectra; this enables molecular control over energy dissipation by varying the fraction of the associative groups. Increasing the volume fraction of the end linear blocks increases the network stiffness by more than 100 times without significantly compromising the extensibility. We created elastomers with Young's moduli ranging from 8 kPa to 8 MPa while maintaining the tensile breaking strain around 150%. Using a high-temperature DIW printing platform, we transformed our elastomers to complex, highly deformable 3D structures without involving any solvent or post-print processing. Our elastomers represent the softest melt reprocessable materials for DIW printing. The developed LAL polymers synergize emerging homogeneous associative polymers with a high fraction of reversible bonds and classical block copolymer self-assembly to form a dual-cross-linked network, providing a versatile platform for the modular design and development of soft melt reprocessable elastomeric materials for practical applications.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

3D Printable Modular Soft Elastomers from Physically Cross-linked Homogeneous Associative Polymers

Kim,

Nian,

Rau

et al. 2024

ACS Polym. Au

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Flexible Cages Enable Robust Supramolecular Elastomers

Xu,

Shao,

Wang

et al. 2024

Advanced Materials

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Advances in modern industrial technology continue to place stricter demands on engineering polymeric materials, but simultaneously possessing superior strength and toughness remains a daunting challenge. Herein, we report a pioneering flexible cage‐reinforced supramolecular elastomer (CSE) that exhibits superb robustness, tear resistance, anti‐fatigue, and shape memory properties, achieved by innovatively introducing organic imide cages (OICs) into supramolecular networks. Intriguingly, extremely small amounts of OICs make the elastomer stronger, significantly improving mechanical strength (85.0 MPa; ∼10‐fold increase) and toughness (418.4 MJ m−3; ∼7‐fold increase). Significantly, we experimentally and theoretically demonstrate the cooperative effect of gradient hydrogen bonds and OICs as flexible nodes, enabling more robust supramolecular networks. In short, our proposed strengthening strategy of adding flexible cages effectively balances the inherent conflict between material strength and toughness, and the prepared CSEs are anticipated to be served in large‐scale devices such as TBMs in the future.This article is protected by copyright. All rights reserved

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The dynamical signature and scaling of supramolecular assemblies

Cai,

Yin

2023

Supramolecular Materials

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Dynamics of Associative Polymers with High Density of Reversible Bonds

Cited by 10 publications

References 65 publications

3D Printable Modular Soft Elastomers from Physically Cross-linked Homogeneous Associative Polymers

3D Printable Modular Soft Elastomers from Physically Cross-linked Homogeneous Associative Polymers

Flexible Cages Enable Robust Supramolecular Elastomers

The dynamical signature and scaling of supramolecular assemblies

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