Supramolecular polymer-assisted manipulation of triblock copolymers: understanding the relationships between microphase structures and mechanical properties

Shentu, Zhexian; Zhang, Zhaoming; Zhao, Jun; Chen, Chuanshuang; Wu, Qian; Wang, Lei; Yan, Xuzhou

doi:10.1039/d1ta02288a

Cited by 23 publications

(9 citation statements)

References 36 publications

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“…In contrast, our group previously utilized the host−guest recognition between benzo-21-crown-7 and a secondary ammonium salt to develop a type of CSPs with great comprehensive performance, while the CSPs started to show an obvious network disintegration at 60 °C owing to the dissociation of host− guest interactions. 42,47 Hence, we envisioned that the structural basis for the excellent thermomechanical stability of our novel CSPs compared to our previously reported CSPs was as follows. Compared with the host−guest interactions, the stronger metal−ligand interactions were inclined to be more stable in bulk state and possess a higher dissociation temperature.…”

Section: Design Synthesis and Structural Characterizationmentioning

confidence: 99%

“…Furthermore, in 2020, we also reported the design and construction of synergistic covalent-and-supramolecular polymers (CSPs), which exhibited stable and robust mechanical performance as CPs, accompanied by inheriting dynamic features such as stimuli-responsiveness and energy dissipation capacity from SPs . Meanwhile, the importation of noncovalent interactions also provides great potential for utilizing CSPs to construct desirable structures with high efficiency . As a consequence, we envision that CSPs would be capable of serving as a platform to fabricate topologically fascinating polymer networks with both favorable mechanical robustness and dynamic properties.…”

Section: Introductionmentioning

confidence: 99%

“…41 Meanwhile, the importation of noncovalent interactions also provides great potential for utilizing CSPs to construct desirable structures with high efficiency. 42 As a consequence, we envision that CSPs would be capable of serving as a platform to fabricate topologically fascinating polymer networks with both favorable mechanical robustness and dynamic properties.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synergistic Covalent-and-Supramolecular Polymers with an Interwoven Topology

Guo

Liu

Zhao

et al. 2022

ACS Appl. Mater. Interfaces

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Network topologies, especially some high-order topologies, are able to furnish cross-linked polymer materials with enhanced properties without altering their chemical composition. However, the fabrication of such topologically intriguing architectures at the macromolecular level and in-depth insights into their structure−property relationship remain a significant challenge. Herein, we relied on synergistic covalent-and-supramolecular polymers (CSPs) as a platform to prepare a range of polymer networks with an interwoven topology. Specifically, through the sequential supramolecular self-assemblies, the covalent polymers (CPs) and metallosupramolecular polymers (MSPs) could be interwoven in our CSPs by [2]pseudorotaxane cross-links. As a result, the obtained CSPs possessed a topological network that could not only promote the synergistic effect between CPs and MSPs to afford mechanically robust yet dynamic materials but also vest polymers with some functions, as manifested by force-induced hierarchical dissociations of supramolecular interactions and superior thermomechanical stability compared to our previously reported CSP systems. Furthermore, our CSPs exhibited tunable mechanical performance toward multiple stimuli including K + and PPh 3 , demonstrating abundant stimuli-responsive properties. We hope that these findings could provide novel opportunities toward achieving topological structures at the macromolecular level and also motivate further explorations of polymeric materials via the way of controlling their topological structures.

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Section: Design Synthesis and Structural Characterizationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synergistic Covalent-and-Supramolecular Polymers with an Interwoven Topology

Guo

Liu

Zhao

et al. 2022

ACS Appl. Mater. Interfaces

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“…(2) The stress decreases with the increase of strain in the field of A–B. The crosslinking points of the molecular chain are recombined with the occasion of large strain, and the supramolecular 45 structure conducive to deformation is formed. (3) In the B‐C section, the reason why the stress increases slowly as the strain grows is the necking phenomenon.…”

Section: Mechanical Propertiesmentioning

confidence: 99%

Molecular dynamics simulation of crosslinking process and mechanical properties of epoxy under the accelerator

Chen

Liu

2022

J of Applied Polymer Sci

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To simulate the crosslinking process of epoxy resin under the accelerator action, the crosslinking system of bisphenol‐A diglycidyl ether (DGEBA) as a monomer, methyl tetrahydro‐phthalic anhydride (MTHPA) as a thermal curing agent and 2,4,6‐tris (dimethylaminomethyl) phenol (DMP‐30) as a thermal curing accelerator has been studied using molecular dynamics (MD) simulation. An algorithm that can construct the high‐crosslinked system with different crosslinking density is completed based on the Perl language, and the subsequent properties are simulated. The results of molecular dynamics simulation show that modulus have an increasing trend, and glass transition temperature (Tg) raises from 325 K to 480 K when crosslinking density is from 0% to 95.5%. Conversely, cohesive energy density lessens from 620 J/cm3 to 170 J/cm3, solubility and Poisson's ratio decrease, and the tensile strength firstly increases and then diminishes. The friction coefficient decreases firstly and then increases, meanwhile, the temperature suddenly adds by 20 K and the relative concentration distribution (RCD) grows by 1.58 times at the contact surface. This study predicts for the crosslinking process and micro mechanical properties in the DGEBA/MTHPA/DMP‐30 system.

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“…From a microscopic point of view, the properties of polymeric materials are defined by their molecular compositions and topological connections. [5][6][7][8][9][10][11][12][13][14][15][16] Along this line, it is almost impossible to program their inherent property profiles because of the inalterable topology that is typically locked at the polymerization stage. As such, much effort has been devoted to developing stimuli-triggered topology-switchable materials with coherently tunable features in recent years.…”

mentioning

confidence: 99%

Thermo‐responsive topological metamorphosis in covalent‐and‐supramolecular polymer architectures

Wang

Zhang

et al. 2022

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Topological metamorphosis represents a powerful approach to modulate the properties of polymers. However, it still remains a major challenge to achieve the tunability of bulk mechanical properties via topological transformation in supramolecular polymer systems. Herein, we couple the covalent polymer and supramolecular polymer in a single system—referred to as covalent‐and‐supramolecular polymer (CSP)—to realize a thermo‐responsive macromolecular metamorphosis. The CSP is able to topologically switch from grafted polymer to cross‐linked network by taking advantage of synergistic dynamic covalent interactions and host–guest interactions. Benefiting from the topologically structural transformation, brittleness intrinsically evolves into toughness in our CSP architectures with minimum change of their molecular compositions from furan–maleimide to anthracene–maleimide linkers. Our work demonstrates that supramolecular polymers are a promising platform to design smart materials not only due to their inherent stimuli‐responsive properties but also because of their abilities in determining bulk mechanical properties of polymers with alterable topological structures.

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Supramolecular polymer-assisted manipulation of triblock copolymers: understanding the relationships between microphase structures and mechanical properties

Abstract: Block copolymers with specific microphase-separated structures are a class of important reprocessable elastomers. Numerous approaches have been applied to modify their structures and properties, whereas incorporating supramolecular polymers into the...

Cited by 23 publications

References 36 publications

Synergistic Covalent-and-Supramolecular Polymers with an Interwoven Topology

Synergistic Covalent-and-Supramolecular Polymers with an Interwoven Topology

Molecular dynamics simulation of crosslinking process and mechanical properties of epoxy under the accelerator

Thermo‐responsive topological metamorphosis in covalent‐and‐supramolecular polymer architectures

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