Ultra-Strong and Highly-Robust Elastomers with Synergistic Multiple Weak Interactions

Ultra-Strong and Highly-Robust Elastomers with Synergistic Multiple Weak Interactions | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Ultra-Strong and Highly-Robust Elastomers with Synergistic Multiple Weak Interactions Jun Xu, Xinshu Sun, Yuchen Hu, Zhiqi Wang, Baohua Guo, Jiaxin Shi This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6802660/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The increasing demand for high-performance elastomers has spurred research aimed at enhancing comprehensive properties. However, challenges such as complex molecular structures and poor understanding of structure-property relationship have hindered the development of advanced elastomers. To address these limitations, we propose a strategy that strengthens the intermolecular interactions via synergistic multiple weak interactions and leverages theoretical calculations. Adoption of symmetric hard segments effectively organizes π-π stacking, which have a positioning effect and lead to an increase in the spontaneous formation efficiency of multiple hydrogen bonds, resulting in ordered hard domains. Thereby, polyurethane elastomers with exceptional properties were successfully developed by using simple and efficient processes, achieving tensile strength of 104.7 MPa and toughness of 460.5 MJ/m³, which surpass substantial numbers of existing materials. These also exhibit superior resilience, thermal, and chemical resistance, as well as anti-relaxation behavior, making them ideal for extreme conditions. Additionally, we employed rigorous ab initio calculations to analyze the structure of specific segments, which convincingly demonstrate the immense impact of even slight changes of molecular structure and segment arrangement on material performance and provide excellent predictive power for material properties. Consequently, this work establishes a novel framework with vast potential for advancing innovation in high-performance materials. Physical sciences/Materials science/Structural materials/Mechanical properties Physical sciences/Chemistry/Chemical engineering Physical sciences/Materials science/Soft materials/Polymers Physical sciences/Materials science/Theory and computation/Atomistic models Physical sciences/Materials science/Soft materials/Organic molecules in materials science elastomer polyurethane hard domains ab initio computation weak interactions Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1. Introduction Due to their excellent toughness, ductility, and exceptional strength, polymeric elastomers have found extensive application prospects in various advanced fields such as the automotive and aerospace industries, soft robotics, and flexible wearable devices [ 1 – 4 ] . Understanding the influence of internal structures on the macroscopic properties of elastomers, and thereby achieving superior overall performance, has long been a momentous challenge. Although numerous specialty elastomers with high strength have been reported [ 5 – 8 ] , unfortunately, these materials often rely on complex molecular designs and intricate synthesis strategies, which hinders the real-world applications of these high-performance elastomers. At the same time, besides enhancing macroscopic mechanical properties of these elastomers such as tensile strength and toughness at room temperature, there has been increasing demands for strong resistance to high temperatures, organic solvents, and chemicals [ 9 , 10 ] . However, achieving a balance between excellent mechanical properties and specialized performance in a single material often requires the use of complicated composite techniques to meet practical requirements [ 11 , 12 ] . It is undisputable that solving these dilemmas requires a deeper understanding of the microstructure and uncovering the essential logical connections between material structures and performance. Nature provides an abundance of remarkably intricate and inspiring structural templates. The imitation and enhancement of various natural elastomeric structures have been extensively reported, such as modifying polymer chain topologies to mimic the structure and mechanical properties of biological elastic tissues [ 13 ] and replicating the microphase-separated structure of spider silk for the development of artificial textile materials [ 14 ] . These examples of high-performance elastomers have demonstrated that emulating the structural features of natural materials, particularly by implementing soft-hard phase separation within a material, is an effective strategy. This approach enables different regions of the material to respond hierarchically to external stimuli, allowing the material to accommodate large-scale macroscopic deformations. In detail, the strength and toughness of elastomers are simultaneously dependent on their ability to rapidly dissipate external energy and the robustness of their local structures. For instance, in a multilayered soft-hard segregated phase structure, the tightly packed hard domains can withstand high stresses and restrict molecular chain slippage, while the soft domains efficiently distribute and transfer stress to the hard domains, preventing excessive localized stress concentration. As a result, this hierarchical phase separation increases the degree of phase separation by improving the strength and density of the hard segment stacking, which is considered to be a key factor in enhancing overall mechanical performances [ 15 – 17 ] . Based on this concept, materials capable of spontaneous phase aggregation and separation due to unique intermolecular interactions have attracted significant interest for their exceptional performance. For example, polyurethane (PU) is a representative biomimetic polymer system with a highly tunable molecular architecture and strong intermolecular interactions. The presence of multiple hydrogen bonds and other complex weak interactions within PU allows for the self-assembly of soft and hard segments, forming phase-separated microscopic structures similar to those found in biological elastomers. This distinctive architecture endows PU with outstanding macroscopic mechanical properties [ 18 , 19 ] . In the development of high-performance elastomers, represented by PU, adjusting the chemical structure of the molecular chains to further enhance intermolecular interactions and improve mechanical performance has also become a common strategy [ 20 ] . However, achieving elastomers with ultra-high strength (e.g., tensile strength exceeding 100 MPa) and comprehensive properties still remains highly challenging, which typically requires the introduction of complex functional groups, structural blending, or cumbersome post-processing techniques to increase the molecular interactions, such as hydrogen bonding, thereby enhancing hard segment stacking. In addition, the understanding of the relationship between multiscale structures and performance is still limited, leading to a lack of effective structural design methods. Based on this premise, we propose a novel strategy to significantly enhance the overall material performance through precise optimization of the molecular chain structure, complemented by accurate theoretical calculations. We argue that, rather than simply increasing the types and quantity of weak interactions in the material, synergistically combining different weak interactions is a more efficient approach, which necessitates fine-tuning specific structures to facilitate the arrangement and stacking of the hard segments. Therefore, we should not only adjust critical structural parameters, including the distribution of hydrogen bonds, the selection of phenyl ring substitution positions, and chain segment flexibility, but also specifically screen and calculate the intermolecular interactions of the different-positioned phenyl ring structures within the hard segments. Innovative and precise quantum chemical calculations were further integrated to validate our viewpoint, providing a comprehensive and intuitive explanation of the structure-property relationship and the origin of the exceptional performance. These results strongly support the efficacy of our precise molecular chain control strategy. It is particularly noteworthy that, unlike the traditional strategy of increasing the complexity of the backbone to enhance weak interaction density in high-performance elastomer synthesis, our approach focuses on a deeper understanding of the microscopic structural arrangement of the segments. In this work, we designed a kind of special PU synthesized from common and inexpensive feedstocks: PTMEG, HDI or IPDI, and phthalic dihydrazide (PDHZ), with the latter two as the core building blocks to construct the hard segment framework of the material. Thus, a variety of nitrogen-hydrogen groups, oxygen-hydrogen groups, and large-area π-π conjugated structures with diverse chemical environments were introduced. This enables the simultaneous localization of various hydrogen bonds and π-π stacking interactions. Additionally, the relative positional relationship between the dihydrazide group and the phenyl ring can be easily fine-tuned, facilitating the study of the effects of structural changes on the promotion of multiple weak interactions and general properties, thus validating our hypothesis. By applying refined structural modifications at the molecular level, we synthesized a series of ultra-strong, high-performance hydrazide-based polyurethanes (HZPU) with highly symmetric hard segment structures using a simple process and a minimal set of commercially available raw materials (only three primary components), achieving a remarkable enhancement in performance compared to structurally similar conventional materials. Via ab initio DFT simulation, we observed hydrogen bond arrangement driven by the localization effect of the π-π stacking of phenyl rings. Unlike traditional high-strength materials that enhance the types and density of hydrogen bonds by introducing complicated hard segment structure, this work focuses more on the combination and synergistic promotion of various weak interactions, thereby improving the efficiency of spontaneous formation of hydrogen bonds. The synthesized representative material exhibits unprecedented mechanical properties, achieving an ultrahigh tensile strength of approximately 104.7 MPa, an elongation at break of ~ 1000%, and exceptional toughness of ~ 460.5 MJ/m². Further investigations confirm that the hierarchical hard segment stacking within the material endows the material with prominent mechanical strength, superior thermal resistance, outstanding relaxation resistance, and remarkable durability under various harsh chemical environments. These attributes significantly enhance and expand its multifunctionality and potential applications. This work not only introduces a novel and remarkable paradigm for elastomer research but also represents a significant step forward in the exploration and optimization of high-performance material systems. 2. Results and Discussion 2.1. Synthesis and Structural Characterization of HZPU Series Initially, hydroxyl-terminated polytetramethylene ether glycols (PTMEG) whose number-average molecular weights ( M n ) equal to 1,000 were selected to form the soft segments. These were then reacted in precise molar ratios with two widely used commercial isocyanates—hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI)—to produce two types of prepolymers. Notably, HDI introduces flexible six-carbon alkyl chains into the product molecules, while IPDI incorporates bulky six-membered cyclohexane rings. Following this, two kinds of different dihydrazides (terephthalic dihydrazide (p-PDHZ) and isophthalic dihydrazide (m-PDHZ)) were used as chain extenders to further polymerize the prepolymers into HZPU macromolecules. Although these two dihydrazides share the same chemical formula, their functional group substitution patterns differ, leading to variations in the conformations of the hard segment chains in the products. Ultimately, products synthesized from HDI and p-PDHZ were successfully obtained and labeled as HDI-pAr 1000 . Additionally, samples HDI-mAr 1000 , IPDI-pAr 1000 , and IPDI-mAr 1000 and other similar products were obtained, collectively forming the HZPU series, in order to enable a detailed comparison of the practical performance of products with different hydrazide substitution positions, and distinct diisocyanate compositions. The most optimal sample was subsequently selected for further analysis, with the overall process illustrated in Fig. 1 a, while the specific synthesis methods, along with additional information and the rest samples, are provided in the supporting information. For HZPU, the incorporation of urea structural units, formed via the reaction between hydrazide groups and isocyanates, provides a robust basis for the formation of diverse, high-density, localized hydrogen-bond clusters [ 21 , 22 ] . As demonstrated in the following parts, under optimal structural configurations, highly symmetric hydrogen-bond networks were generated, correlating with the prominent macroscopic properties of the resulting samples. Figure 1 b clearly demonstrated the overall microscopic structure of the HZPU samples. Four samples (HDI-pAr 1000 , HDI-mAr 1000 , IPDI-pAr 1000 , and IPDI-mAr 1000 ) were analyzed using Fourier-transform infrared spectroscopy (FTIR) to identify and compare hydrogen bonding interactions. The spectral region between 1600 and 1750 cm⁻¹ was deconvoluted into seven distinct peaks. Specifically, the peaks at 1725 cm⁻¹ (Peak I) and 1690 cm⁻¹ (Peak III) correspond to free urethane and urea carbonyl vibrations, respectively. Peaks at 1710 cm⁻¹ (Peak II) and 1670 cm⁻¹ (Peak IV) are attributed to urethane and urea carbonyls involved in random, disordered hydrogen bonds, while the remaining peaks represent carbonyl groups forming ordered hydrogen bond clusters [ 21 ] . Integration of the peak areas revealed that the sample derived from HDI and p-PDHZ (HDI-pAr 1000 ) exhibited the highest proportion of hydrogen-bonded carbonyl groups, up to 73.62%. Among these, about 51.56% were associated with ordered hydrogen-bonded carbonyls, clearly surpassing the other samples (49.19%, 47.79% and 48.49% for HDI-mAr 1000 /HDI-mAr 1000 /HDI-mAr 1000 , respectively, refer to Fig. 2 a-b and Figure S1 -2 ). These findings indicate that HDI-pAr 1000 contains a dense network of ordered hydrogen bonds, suggesting a more regular hard-segment structure. Figure 2 c-f and Figure S3 further illustrate the FTIR spectra of the four samples under varying temperatures, along with the corresponding synchronous and asynchronous two-dimensional (2D) infrared spectra. Using Noda’s 2D IR correlation theory [ 23 – 24 ] , it is demonstrated that for HDI-pAr 1000 , the relative proportion of disordered hydrogen bonds and amorphous carbonyls to ordered hydrogen bonds remained stable as the temperature increased. This highlights that the internal hydrogen-bonding network of HDI-pAr 1000 is robust and retains stability over a certain temperature range. In contrast, the other samples exhibit significant transitions in carbonyl groups with rising temperatures, shifting from ordered hydrogen-bonded urethane and urea carbonyls to disordered or free carbonyls, alluding to inferior hydrogen bond stability, with noticeable breakdowns or conversions occurring due to temperature changes. In summary, FTIR results preliminarily signify that HDI-pAr 1000 possesses a dense and highly stable hydrogen-bonding network, suggesting the presence of a high-strength and localized hard-segment structure. To further elucidate the differences in phase structures among the prepared samples, small-angle X-ray scattering (SAXS) measurements were conducted on the samples in both their pristine and stretched states, as shown in Fig. 2 g-h and Figure S4-5 . Based on the physical relationship between the peak position 𝑞 of the scattering signal and the corresponding size 𝑑 of the aggregated regions [ 25 ] , given by the formula: $$\:\begin{array}{c}d=\frac{2\pi\:}{q}\#2-1\end{array}$$ Following this, the estimated dimensions of the stacked hard segment regions in different HZPU samples were determined. For HDI-pAr 1000 , the scattering peak position q is observed at 0.083 Å −1 , corresponding to an average dimension of the aggregated hard segment regions (represented as the mean inter-segmental spacing) of approximately 7.57 nm. This value is notably larger than that of other samples, such as IPDI-pAr 1000 , where the calculated hard segment dimension is 5.11 nm. This suggests that HDI-pAr 1000 forms a more extensive hard segment domain. Additionally, the scattering peak intensity of HDI-pAr 1000 is relatively higher, and its two-dimensional SAXS pattern in the original state exhibits apparently more pronounced scattering features compared to other samples. This indicates that the hard segment regions in HDI-pAr 1000 not only span a larger area but also exhibit greater structural regularity and a higher hydrogen bond density. At the initial stage of the tensile process, the scattering peak of HDI-pAr 1000 shifts further to the left while maintaining a high peak intensity. This reveals that during stretching, the molecular chains undergo alignment, and the hard segment stacking regions continuously undergo orientation while retaining strong resistance to tensile stress, resulting in further expansion of the scattering area size. Only under extreme stretching do the hard domains begin to break down. In contrast, for the other samples, the scattering peak intensity decreases noticeably even at the early stages of stretching, suggesting that their hard domains have relatively weaker resistance to tensile stress, with significant disruption occurring early in the stretching process. SAXS results obtained under tensile strain demonstrate that HDI-pAr 1000 maintains a high density and structurally regular extensive hard segment domain over a range of strain levels, underscoring its remarkable stability and responsiveness. Dynamic mechanical analysis (DMA) experiments (Fig. 2 i-l) further confirm that HDI-pAr 1000 exhibits multiple distinct transition points: A single peak observed at -59.5°C corresponds to the glass transition temperature ( T g ) of the soft segments within the molecular chains. In addition, a more complex peak shape appears in the temperature range above 100°C, corresponding to the motion of the hard segments. Notable peaks appear at 112.3°C and 161.6°C, indicating cascaded responses in the hard segment interactions within the sample near these temperature points. In comparison, the other samples exhibit a clear decline in the storage modulus with increasing temperature, lacking a stable modulus plateau, and show a vague loss tangent peak at high temperatures. This suggests that, compared to HDI-pAr 1000 , the hard segment interactions in the other samples are weaker, leading to higher mobility and activity with increasing temperature, which adversely affects the macroscopic mechanical properties. Furthermore, at temperatures exceeding 200°C, HDI-pAr 1000 maintains a storage modulus of over 10 MPa and preserves a stable macroscopic form, demonstrating thermal resistance even comparable to that of thermosetting polymers with chemical crosslinking structures. In contrast, the other samples completely soften and flow below 175°C. In conclusion, compared to the other samples, HDI-pAr 1000 possesses a higher glass transition temperature of its hard segments and superior thermal resistance, highlighting the presence of robust and stable hard domains. All these characterizations mentioned above suggest that HDI-pAr 1000 , compared to other formulations, is likely to possess superior mechanical and physical properties. To investigate the underlying structural distinctions responsible for the formation of its high-performance hard segment regions, more detailed theoretical simulations are analyzed and discussed in subsequent sections. 2.2. Structural Theoretical Calculation and Simulation of HZPU Series The characterization results of the HZPU series samples clearly demonstrate that HDI-pAr1000 possesses an exceptionally stable hard domains, sparking curiosity and interest in exploring the differences in the aggregated structures of various HZPU molecular chains. Computational chemistry and simulation serve as powerful tools for uncovering structures and behaviors at a fundamental molecular level and have been widely employed in the analysis of various materials in previous studies. Unfortunately, there is still a lack of a systematic and convincing comprehensive analysis process for polymer systems, especially PU, due to the complex and dense interactions within the system. Additionally, the high molecular weight and the diversity of functional groups limit the precision of computational simulations. Currently, common simulation approaches involve using coarse-graining (CG) methods to simplify the molecular chain structure, expecting to strike a balance between accuracy and computational time, or employing empirical molecular dynamics methods to roughly calculate macroscopic thermodynamic quantities for specific molecular chain conformation [ 21 , 22 ] . However, the former approach inevitably overlooks certain fine interactions when simplifying the structure, particularly with regard to the arrangement and strength of various hydrogen bonds in elastomers, which cannot be precisely predicted. In the latter approach, the specific molecular chain conformations often need to be subjectively assigned, which may not reflect the actual configurations of the molecular chains within the system, while empirical molecular dynamics methods always limit the accuracy of the simulations as well. A more systematic and rigorous scheme would be preferred to conduct extensive conformational searches and first-principles calculations on elastomer molecular chains at a high precision level, but this is prohibitively expensive. To address these issues, we adopt a more efficient method for theoretical calculations and behavior predictions for HZPU. We propose that, as previously mentioned, the dominant interactions within HZPU should be multi-hydrogen bonding and π-π stacking, primarily provided by the conjugated benzene ring system and highly electronegative atoms in the hard segment of the molecular chain. Therefore, the macroscopic performance and characteristics of the system are strongly correlated with the changes in the internal hard segment structure. Consequently, extracting and simulating the hard segment part of the molecular chain in depth, rather than performing direct calculations on the entire molecular chain, can innovatively reflect the influence of the HZPU molecular structure on its performance to a large extent, all within a limited and acceptable computational time frame. Hence, in our theoretical calculation work, the hard segment regions of the four samples were individually extracted, while the connected soft segment regions were replaced with methyl groups. Among them, the molecular structure formed by the reaction of p-PDHZ with HDI was further classified into two models with different symmetries ( cis and trans ) based on the orientation of the carbonyl groups attached to the benzene ring. This classification was carried out to precisely study the subtle differences in the molecular structure and their impact on the hard segment interactions. It should be noted that the HDI-pAr 1000 material obtained through actual synthesis is an isomeric mixture containing both cis and trans molecular structures. Following this approach, five distinct molecules of hard segments were obtained: three models formed with HDI as the monomer, each consisting of 84 atoms, and two molecules formed with IPDI as the monomer, each consisting of 104 atoms. All the structures are shown in Fig. 3 a. With the aid of density functional theory (DFT), renowned for its high precision and accuracy, ab initio methods were employed to conduct a detailed analysis of the five molecules. The entire computational work was performed using the xtb software [ 27 , 28 ] and Gaussian 16 Version A.03 [ 29 , 30 ] , with detailed steps provided in the supporting information. Firstly, the five molecules were optimized after a large-scale and comprehensive conformational searching process, and single-point energy calculations were performed on the optimized structures. In the following text, the five molecules are denoted as I to V , corresponding to the hard segment of HDI-pAr n ( cis ), HDI-pAr n ( trans ), HDI-mAr n , IPDI-pAr n and IPDI-mAr n , respectively, with their specific structures shown in Fig. 3 a. Based on this, structural optimizations were carried out for the dimers of the five molecules, leading to the lowest-energy dimer configurations and the corresponding dimer interaction energies. The results show that the interaction energy of molecule I is -72.65 kcal/mol, which is significantly stronger than that of the other molecules. From the optimized structure, it can be observed that the cis -terephthalic dihydrazide and HDI combination enables the hard segments to form a prominent π-π stacking interaction as well as various types of hydrogen bonding. The benzene rings involved in the π-π stacking interaction play a good localization role, promoting the formation of a multi-type hydrogen bond network, which expedites effective packing of the hard segments and enhances their performance. In detail, when the cis -configured HDI-pAr hard segments stack in an alternating orientation, the planar π orbitals formed by the benzene rings and amide groups achieve effective overlap. This overlap strengthens the interaction between hard segments and organizes the spatial configuration of urea and carbamate groups, restricting them within appropriate regions. As a result, the formation of ordered hydrogen bonds is greatly facilitated, increasing the density of weak interactions between atoms and yielding a symmetrically centered and refined structure, as shown in Fig. 3 b. In contrast, molecule II , based on trans -terephthalic dihydrazide, does not form the optimal structure mentioned above. This is because the molecular structure causes the planar π orbitals formed by the amide and benzene rings to twist when both interactions are simultaneously formed, leading to an increase in energy. Compared to the molecules based on HDI, molecules IV and V , due to the steric hindrance introduced by the six-membered ring of IPDI, also have difficulty in forming a structure similar to molecule I . Therefore, based on the theoretical calculations, it is revealed that the use of terephthalic dihydrazide and HDI as polymerization monomers leads to samples (HDI-pAr n ) with ordered packing of hard segments due to the cis -terephthalic dihydrazide units, resulting in performance improvements distinct from those of ordinary HZPU series. Consequently, it is expected that HDI-pAr n will exhibit exceptional comprehensive performance. Next, an energy decomposition based on dispersion-corrected DFT methods [ 31 ] was performed for the five dimer configurations. Specifically, the interaction energy of the dimers was decomposed into the following energy components: $$\:\begin{array}{c}{\varDelta\:E}_{int}={\varDelta\:E}_{e}+{\varDelta\:E}_{ex-rp}+{\varDelta\:E}_{o}+{\varDelta\:E}_{d}\#2-2\end{array}$$ Among them, ∆E e and ∆E o represent the electrostatic interaction energy and the orbital interaction energy between the dimers, respectively, and ∆E d represents the dispersion-corrected energy. ∆E ex−rp describes the DFT functional-related corrections and repulsive effects between the dimers, which negatively affect the energy lowering during dimer interaction. In the polyurethane system, multiple hydrogen bonds are weak interactions primarily driven by electrostatic forces, while π-π interactions are considered as dispersion interactions. Therefore, the value of ∆E e can partially reflect the hydrogen bonding density in the five dimers, while ∆E d can measure the strength of the π-π interactions within the dimer. All computational results are presented in the Table 1 , Fig. 3 c and Figure S6 . It can be observed that the dimer of molecule I indeed exhibits relatively strong dispersion interactions, indicating good π-π stacking, which contributes to the structural regularization of the dimer and further enhances the density of multiple hydrogen bonds (compared to the other molecules, ∆E e decreased by approximately 14 kcal/mol). Comparing the dimers of molecules IV and V containing IPDI components, it is noted that although the dimer formed by molecule IV also shows strong dispersion interactions, these interactions primarily arise from the overlapping of bulky carbon rings in the molecule rather than π-π stacking. As a result, the influence on the overall structure of the hard segment is smaller, and the enhancement in multiple hydrogen bond density is not significant (compared to molecule V , ∆E e decreased by approximately 7 kcal/mol). The energy decomposition results show that, in structures with a similar number of hydrogen bonding sites and configurations (e.g., molecules I , II , and III ), the actual number and strength of hydrogen bonds (represented by ∆E e ) are positively correlated with ∆E d , which mainly represent the contribution of π-π stacking. The ∆E e and ∆E d values for molecule I are higher than those of all other dimers, providing in-depth evidence that HDI-pAr n ( cis ) simultaneously exhibits π-π stacking interactions and multiple hydrogen bonding, with the former promoting the formation of the latter. Specifically, due to the strong π-π stacking effect, the hard segments can spontaneously recognize and assemble. Simultaneously, as the π-π stacking is formed, the polar groups and hydrogen atoms on both sides of the phenyl rings in the hard segment also reach appropriate spatial positions. As a result, compared to similar elastomer systems that only contain hydrogen bonds or lack the ability to form hydrogen bonds together with π-π stacking, the formation of multiple hydrogen bonds becomes much easier and more efficient, particularly when the material undergoes dynamic behavior and spontaneous recovery. This effect allows our material to achieve high density of hydrogen bonds and hard segment stacking, which is beneficial for macroscopic performance. Figure 3 d-e clearly visualizes the considerable weak interactions and the dispersion energy contributions from individual atoms within the dimer of molecule I . In contrast, the visualizations of all other dimers can be found in Fig. 3 d-e and Figure S7-14 . Table 1 The ab initio calculation results for the dimer energies of the five hard segment molecules. HDI-pAr n ( cis ) HDI-pAr n ( trans ) HDI-mAr n IPDI-pAr n IPDI-mAr n Total Dimer Binding Energy (kcal/mol) -90.52 -76.36 -81.71 -87.87 -84.21 ∆E e (kcal/mol) -114.76 -99.86 -100.38 -111.87 -104.59 ∆E ex−rp (kcal/mol) 160.04 171.71 124.31 171.81 129.48 ∆E o (kcal/mol) -50.38 -43.65 -42.64 -47.26 -45.95 ∆E d (kcal/mol) -85.42 -74.55 -63.01 -100.54 -63.15 Additionally, previous work highlights that in polymeric elastomers with spontaneous soft and hard segment separation, well-stacked hard segment regions often endow the corresponding materials with remarkable robustness and solvent resistance [ 32 ] . Inspired by this, we conducted simulations to analyze the dissolution performance of the five dimers in various solvents, further elucidating the performance differences within the HZPU elastomer series and their potential for specialized applications. Therefore, an implicit solvent model (SMB) [ 33 ] was applied to calculate the total energy reduction values of the five dimers in different solvent environments, in order to assess the effect of different hard segment compositions on the solubility performance of the samples. Three representative solvents (dimethylformamide (DMF), tetrahydrofuran (THF), and dichloromethane (DCM)) were used in the calculations, with the results shown in Fig. 3 f. According to the results, the dimer formed by molecule I possesses the relatively lowest energy reduction in all three solvents, indicating that the hard segment region of HDI-pAr 1000 ( cis ) has the strongest resistance to dissolution in these solvents. This further reveals the stacking strength of the hard segments and provides theoretical support for the sample's excellent solvent endurance. 2.3. Mechanical Properties Evaluation of HZPU Series The physical characterization tests of the HZPU series mentioned earlier reveal that HDI-pAr 1000 possesses a unique and novel robust hard segment stacking structure, while detailed theoretical calculations further support that HDI-pAr 1000 , based on its distinctive hard segment chemical structure, can spontaneously form an attractive highly-symmetric cluster network, endowing it with extraordinary macroscopic mechanical properties. To verify our hypothesis, we conducted a series of diverse mechanical performance tests on the HZPU series samples. Tensile experiments were performed on the four representative samples with varying hard segment structures (HDI-pAr 1000 , HDI-mAr 1000 , IPDI-pAr 1000 , and IPDI-mAr 1000 ), as shown in Fig. 4 a. Among the samples, HDI-pAr 1000 exhibits extraordinary mechanical properties, with maximum engineering tensile stress reaching 104.7 MPa, elongation-at-break of 1000% (ten times the original sample length, as shown in Fig. 4 b), and toughness up to 460.51 MJ/m³. Its true stress exceeds 1 GPa, far surpassing the performance of the other samples and aligning well with the results from structural characterization and quantum mechanical simulations. The tensile curves also reveal that, despite the only structural difference between HDI-pAr 1000 and HDI-mAr 1000 being the substitution position on the benzene ring within the hard segments, HDI-pAr 1000 demonstrates significantly superior mechanical properties and distinct tensile curve. In contrast, the tensile curves of IPDI-pAr 1000 and IPDI-mAr 1000 nearly overlap, indicating similar mechanical performance. This suggests that the benzene ring substitution position has negligible influence on the properties of HZPU prepared with IPDI, whereas the unique and highly regular hard segment structures within HDI-pAr 1000 strongly enhance its macroscopic performance. As shown in Fig. 4 c, under natural conditions, an HDI-pAr 1000 strip sample weighing only about 0.1g can stably hang weights larger than 5 kg (equivalent to 50,000 times its own weight) without fracture, demonstrating truly remarkable mechanical properties. Figure 4 d further illustrates the elastic recovery of the HZPU series samples. After stretching all the HZPU strips to 400% of their original length and allowing sufficient time for natural recovery, all samples return to a length close to their original state. Among them, the HZPU samples prepared with HDI show a more complete recovery, indicating that the long alkyl chain structure in HDI provides more freedom for molecular chain movement compared to IPDI, resulting in superior recovery performance. Compared with previous comprehensive studies on high-performance non-heterocyclic PU elastomers, HDI-pAr 1000 , which owns an extremely simple structure and does not require a complicated preparation process, possesses the highest mechanical strength known to date astonishingly [ 34 – 47 ] (Fig. 4 e). It not only surpasses various crosslinked adaptive network (ANs)-based elastomers that rely on multiple weak interactions but also outperforms ultra-strong spider silk and other bioinspired high-performance materials with similar architectures. Notably, studies using materials and structures closely resembling those in our samples are highlighted in the figure for direct comparison. By finely tuning the specific chemical structures within the hard segments, we successfully achieve a substantial performance improvement over these existing reports and provide a detailed theoretical explanation of the underlying mechanisms. This strongly validates the feasibility and potential of precision structural adjustments in polymer elastomers. Furthermore, compared to many high-performance elastomer manufacturing methods, the raw materials and fabrication processes for HZPU are relatively simple, further augmenting its scalability and adaptability for broader applications. As shown in Fig. 4 f, the component score is defined as the number of types of raw materials required to prepare the corresponding material (excluding catalysts and solvents, only counting the reactants that form the main molecular structure of the material). When compared to several recently reported representative ultra-high-strength elastomers (not limited to PU-based materials), HDI-pAr 1000 , with a component score of only 3 and an extremely straightforward preparation process, demonstrates mechanical performance comparable to the best-known elastomers with component score equal to 4. It can also rival the performance of more complex elastomers with component score equal to 5 or more, while significantly outperforming other high-performance materials with the same component score (3). This achieves a perfect balance between preparation complexity and apparent performance, setting a new record for constructing ultra-strong elastomer using an uncomplicated approach. Further mechanical tests were conducted to comprehensively evaluate the in-depth properties of the HZPU samples. Figures 4 g and Figure S19-21 display the results of cyclic tensile experiments. HDI-pAr 1000 and other samples were stretched to 500% strain at a rate of 50 mm/min, then returned to their original length at the same rate. After allowing the samples to naturally recover at different times and temperatures during the stretching process, a secondary tensile test was performed to assess the samples' rebound capacity and stability. The tests revealed that HDI-pAr 1000 achieved an exceptionally high energy loss value, reaching 54.8 MJ/m³, as represented by the hysteresis loop formed by the return curve, which reflected the material's extraordinary energy dissipation ability. Meanwhile, after a short period of rest, the stretched HDI-pAr 1000 strip was able to recover most of its performance. Notably, when placed in a 70°C oven for just 5 minutes, the energy loss modulus recovered to 48.6 MJ/m³ (88.7% of the original value). Moreover, the tensile stress corresponding to the maximum strain (500%) showed no significant change, demonstrating that HDI-pAr 1000 not only possesses powerful stress dissipation capabilities but also exhibits excellent rebound and damage recovery abilities. This makes it a highly reliable fatigue-resistant elastomer, owing to the ease with which the hydrogen bond network, enhanced by the positioning effect of the benzene rings, spontaneously assembles reversibly under stretching conditions. Since the hard segment stacking in HZPU primarily relies on weak interactions, such as multiple hydrogen bonds and π-π stacking, the physical crosslinking within the material is characterized by variable and reversible properties. This allows for continuous stretching at different temperatures, enabling the observation of the material's relaxation behavior and providing a means to assess the stability of the physical crosslinking within the hard segments. The relaxation time (τ) for all samples is defined as the time required for the internal stress to decrease to 1/e of the initial tensile stress, from which the corresponding relaxation activation energy ( E a ) is calculated using the Kohlrausch-Williams-Watts relaxation theory and the Arrhenius equation [ 60 ] . Basically, higher absolute value of relaxation activation energy indicates stronger stacking and crosslinking of the hard segments, as well as better thermal stability. Detailed experimental results are shown in Fig. 4 h-i and Figure S16-18 . HDI-pAr 1000 exhibits a strikingly high relaxation activation energy (131.62 kJ/mol), which even far exceeds that of many dynamic covalently crosslinked elastomers based on chemical bonding that have been previously reported [ 61 ] , demonstrating the exceptional hard segment cluster structure within HDI-pAr 1000 provides a level of physical crosslinking that rivals the strength of chemical bonding. Moreover, HDI-pAr 1000 was unable to reach the corresponding relaxation level within a limited time at 75°C, while further extrapolation using the Arrhenius equation suggests that its theoretical relaxation time at room temperature (25°C) reaches an astonishing 1.4×10⁹ seconds, equivalent to approximately 45 years, highlighting its excellent high-temperature resistance and anti-relaxation properties, which aligns with our expectations. Figure 4 j further show the results of the HDI-pAr 1000 sample in the split-Hopkinson pressure bar test. As the strain rate of the dynamic load increases over an ultra-short period, the maximum stress rises significantly. At a high strain rate of 5000 s⁻¹, the peak stress reaches up to 320 MPa, with the overall stress level much higher than that of various elastomeric materials previously reported [ 62 – 64 ] . This illustrates that HDI-pAr 1000 exhibits exceptional impact resistance, with the ability to rapidly dissipate stress in a short period, showcasing strong local resistance to failure. In summary, the results of all the mechanical experiments demonstrate that the HZPU series, particularly HDI-pAr 1000 , possesses outstanding and comprehensive mechanical properties, impressively surpassing numbers of conventional elastomers. These results further denote the accuracy of theoretical simulations and physical structural characterization, confirming the success of the precise polymer structural control strategy. 2.4. Performance of Optimal HDI-pAr 1000 under Various Harsh Environments and Derived Applications Attributable to its highly stable and extensive hard segment domains, HDI-pAr 1000 exhibits not only extraordinary macroscopic mechanical properties but also remarkable stability under conditions that are exceedingly challenging for conventional thermoplastic elastomers. Specifically, tensile tests were performed on the samples at various temperatures, as shown in Fig. 5 a. The results reveal a gradual decline in maximum engineering stress with increasing temperature, which is a predictable outcome stemming from enhanced molecular chain mobility. Nevertheless, even after thermal equilibration at 100°C, the material maintains a relatively high tensile stress (~ 51.4 MPa) and a wide strain range. It is worth noting that among many widely applied or reported high-performance elastomers mentioned earlier, a considerable number fails to achieve tensile strengths exceeding 50 MPa under ambient conditions. This suggests that even at elevated temperatures, HDI-pAr 1000 maintains mechanical properties that rival or even surpass those of similar materials, underscoring its exceptional potential for high-temperature applications. Interestingly, the tensile test results at 75°C and 100°C are nearly identical, indicating that HDI-pAr 1000 possesses a tiered temperature response, with significant loosening of the hard segments occurring only beyond 100°C. The results from the previous DMA tests also confirm this observation: in the temperature-dependent DMA data for HDI-pAr 1000 , the second loss tangent peak at 112.3°C suggests that the hard segment regions within the material begin to undergo a transition at this temperature, which lies higher than 100°C. Additional experiments, presented in Fig. 5 b, involved reprocessing crushed HDI-pAr 1000 samples at elevated temperatures (> 160°C). The reprocessed samples exhibited no notable changes in macroscopic appearance, transparency, or mechanical properties, demonstrating that the hard segment structures can reorganize efficiently without compromising performance. These findings highlight the exceptional recyclability of HZPU at high temperatures, significantly expanding its application scenarios. The results of the aforementioned theoretical simulations not only confirmed the presence of highly distinctive and orderly hard segment clusters within HDI-pAr 1000 , but also predicted its resistance to dissolution using an implicit solvent model. This was further validated through a series of experiments. Compared to other samples in the HZPU series, HDI-pAr 1000 also demonstrates outstanding chemical durability and solvent resistance, allowing for its application as a high-performance material in extreme environments. Figures 5 c and Figure S 22-28 present the performance variations of four HZPU samples after exposure to strong acidic, alkaline, and high-concentration saline solutions. The samples were immersed in 1 mol/L hydrochloric acid, 1 mol/L sodium hydroxide, and 2 mol/L sodium chloride solutions for up to 9 hours. Afterward, they were retrieved, thoroughly dried, and weighed to evaluate mass loss before tensile testing. The results indicate that all samples maintained excellent resistance to acid and saline treatments. However, when subjected to alkaline conditions, all samples except HDI-pAr 1000 underwent severe degradation, with some failing to retain a recoverable shape. This outcome aligns with the well-known catalytic effect of bases in accelerating the hydrolysis of polyurethane materials. In contrast, HDI-pAr 1000 showed minimal deformation in post-treatment, retaining its structural integrity with only slight warping and minor mass loss. Furthermore, its mechanical strength and elongation at break remained near pre-treatment levels, emphasizing its robustness under harsh chemical conditions. A similar trend emerged when organic solvents were introduced (Figs. 5 d and Figure S 29). Tests utilized three representative solvents: tetrahydrofuran (THF), dichloromethane (DCM), and dimethylformamide (DMF), also partially correspond to theoretical simulations. HDI-pAr 1000 was immersed in these solvents for three days before drying. Impressively, the material retained stability across all three solvents. Even when exposed to elevated temperatures in DMF, HDI-pAr 1000 preserved its mechanical properties over a prolonged period (3 hours) with only slight reductions. The shredded HDI-pAr 1000 was further immersed in DMF for up to thirty days, during which it still did not dissolve, only experiencing slight swelling. By contrast, other HZPU samples dissolved entirely in DMF at room temperature within just one hour. The unparalleled structural strength and chemical resistance of HDI-pAr 1000 ’s hard segments have been firmly validated through these experiments. Given the excellent special properties of HDI-pAr 1000 , we believe it can be applied in a variety of important scenarios where high-performance novel materials are required (Fig. 5 e). These include utilizing its anti-relaxation and high stability properties for construction raw materials or long-term biomedical implants; leveraging its excellent thermal resistance for high-temperature sensors or specialized thermal insulation linings; exploiting its exceptional mechanical strength for aerospace materials or high-performance biomimetic grippers; and taking advantage of its outstanding chemical resistance for manufacturing anti-corrosion devices or protective inner linings for transport pipelines, among others. For example, HDI-pAr 1000 can be used as an excellent circuit encapsulation material. After encapsulation, the circuit with a complex shape can withstand significant bending while maintaining stable performance (Fig. 5 f). This is due to the high toughness and strong energy dissipation ability of the HZPU material. When the encapsulated circuit is bent and immersed in simulated seawater (a 2 mol/L mixed solution of sodium chloride and magnesium chloride, with the actual electrolyte concentration much higher than that of real seawater), the encapsulation material’s excellent resistance to saline solutions allows the circuit to remain stable and conductive for over three days without any signs of corrosion (Fig. 5 g). Another very interesting and practically significant example is shown in Fig. 5 h, leveraging the material's inherent advantages of easy processing, re-molding without performance loss. A special-shaped pneumatic finger was designed and easily manufactured. This device can regulate its opening and closing states, as well as the force of closure, by controlling the airflow entering it. In practical use, thanks to the high toughness and elasticity of HDI-pAr 1000 , the pneumatic finger can precisely grasp and release fragile block-shaped tofu (a kind of common Chinese soft food product), without any damage to the tofu after gripping and releasing, as seen in Fig. 5 i. Additionally, for heavier objects, such as a 500g weight, the pneumatic finger can easily lift them up and maintain the position for a long time in extreme conditions, including 15% hydrochloric acid solution or dichloromethane, as shown in Fig. 5 j. All behaviors are highly similar to human fingers, with even greater stability and resistance to harsh conditions. In summary, these applications not only demonstrate the versatility and simplicity of using HZPU in various special environments but also further validate and showcase their ultra-high strength, diverse special properties, and remarkable resistance to harsh environmental conditions. These findings reveal the potential of the material as a candidate solution for addressing numerous practical challenges, shedding light on the long-standing issue of the lack of suitable, high-performance elastomeric materials for such applications. 3. Conclusion In contrast to the previous approaches typically increasing weak interaction sites between molecular chains by incorporating complicate local chemical structures, in this work we propose an innovative strategy via fine-tuning and optimizing local chemical structures to cooperatively promote various weak interactions, such as π-π stacking and multiple hydrogen bonds. The phenyl ring units substituted with hydrazide groups were chosen as the core structural component due to their abundant hydrogen bonding sites, localized and stackable strong π orbital effects, and excellent tunability of local structures and symmetry. Comprehensive quantum chemical calculations based on DFT theory were innovatively applied to thoroughly investigate and compare the interactions within the hard segments of the material. The results reveal that, in the cis hard segment of HDI-pAr 1000 , symmetric molecular structures allow for the local molecular chains to adopt configurations that facilitate long-range ordering and the simultaneous formation of multiple weak interactions. The benzene ring-dominated π-π stacking serves as an anchoring and positioning mechanism, thereby facilitating the efficient and spontaneous formation of multiple hydrogen bonds, thereby resulting in efficient energy dissipation and extraordinary properties. Consequently, the obtained elastomer exhibits unparalleled tensile strength (104.7 MPa) and toughness (460.5 MJ/m³), along with excellent performance in various aspects, such as thermal resistance (tensile strength above 50 MPa at 100°C), strong elastic recovery (88.7% recovery of the energy loss modulus after 5 minutes at 70°C), and anti-relaxation properties (relaxation activation energy of 131.62 kJ/mol, with a relaxation time of 45 years at room temperature). Further experiments confirmed that the elastomer also demonstrates remarkable resistance to extreme chemical conditions, such as strong acid, strong base, concentrated salt solutions, and various organic solvents, paving the way for its potential use as a high-performance specialty elastomer in extreme environments. In conclusion, through the synthesis of the unparalleled high-performance HZPU material and a series of solid theoretical analyses, our strategy of precise microstructure optimization of polymer elastomers combined with computational chemistry for mechanistic explanation and prediction has proven to be both innovative and effective. This approach provides a directional guidance for studying and exploiting the complex interactions within polymers. It is particularly noteworthy that, by logically combining theoretical simulation calculations with experiments according to the method employed in this work, the associations and synergistic effects of different interactions can be clearly evaluated and adjusted, thus accelerating the development of high-performance materials. 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He, S. Xuan, X. Gong, Matter 2022 , 5 , 2265. Additional Declarations There is NO Competing Interest. Supplementary Files SupportInformation.docx Supporting Information: Ultra-Strong and Highly-Robust Elastomers with Synergistic Multiple Weak Interactions TableofContent.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6802660","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":471868944,"identity":"9a86f455-84d4-4c71-a738-37128467bf6e","order_by":0,"name":"Jun Xu","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0003-2345-0541","institution":"Tsinghua University","correspondingAuthor":true,"prefix":"","firstName":"Jun","middleName":"","lastName":"Xu","suffix":""},{"id":471868945,"identity":"1a88506f-f0cb-416a-a53f-05301bb4fd50","order_by":1,"name":"Xinshu Sun","email":"","orcid":"https://orcid.org/0009-0004-0691-0635","institution":"Tsinghua University","correspondingAuthor":false,"prefix":"","firstName":"Xinshu","middleName":"","lastName":"Sun","suffix":""},{"id":471868946,"identity":"b733196b-65b2-4b24-b4ac-b5d4b85fc47a","order_by":2,"name":"Yuchen Hu","email":"","orcid":"","institution":"Tsinghua University","correspondingAuthor":false,"prefix":"","firstName":"Yuchen","middleName":"","lastName":"Hu","suffix":""},{"id":471868947,"identity":"97e072d0-7c96-4886-8118-a252f6aa5694","order_by":3,"name":"Zhiqi Wang","email":"","orcid":"","institution":"Advanced Materials Laboratory of Ministry of Education (MOE), Department of Chemical Engineering, Tsinghua University","correspondingAuthor":false,"prefix":"","firstName":"Zhiqi","middleName":"","lastName":"Wang","suffix":""},{"id":471868948,"identity":"4a49a336-4ba4-4881-b1cd-3272446c8f78","order_by":4,"name":"Baohua Guo","email":"","orcid":"","institution":"Advanced Materials Laboratory of Ministry of Education (MOE), Department of Chemical Engineering, Tsinghua University","correspondingAuthor":false,"prefix":"","firstName":"Baohua","middleName":"","lastName":"Guo","suffix":""},{"id":471868949,"identity":"9e6e6d1d-ba71-4e9b-a64f-ab9c1706cc20","order_by":5,"name":"Jiaxin Shi","email":"","orcid":"https://orcid.org/0000-0002-8854-1367","institution":"Tsinghua University","correspondingAuthor":false,"prefix":"","firstName":"Jiaxin","middleName":"","lastName":"Shi","suffix":""}],"badges":[],"createdAt":"2025-06-02 13:35:41","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6802660/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6802660/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":84764867,"identity":"08c67b6e-062b-42e1-b93f-f49878bfbf08","added_by":"auto","created_at":"2025-06-17 06:54:36","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":2209956,"visible":true,"origin":"","legend":"\u003cp\u003e(a)Synthetic routes and products of HZPU series. \u0026nbsp;(b)schematic illustration of the phase separation structure between the soft and hard segment regions within the HZPU series.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-6802660/v1/7e083d1651d00ea3d294efab.png"},{"id":84764084,"identity":"cb8258d7-ae15-44ae-a3c1-47d540cc5735","added_by":"auto","created_at":"2025-06-17 06:46:36","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1866712,"visible":true,"origin":"","legend":"\u003cp\u003e(a, b)FTIR spectra between 1600-1750 cm\u003csup\u003e-1\u003c/sup\u003e of HDI-pAr\u003csub\u003e1000 \u003c/sub\u003e(a) and IPDI-pAr\u003csub\u003e1000 \u003c/sub\u003e(b). (c, d)2D synchronous FTIR patterns between 1600-1750 cm\u003csup\u003e-1\u003c/sup\u003e of HDI-pAr\u003csub\u003e1000 \u003c/sub\u003e(c) and IPDI-pAr\u003csub\u003e1000 \u003c/sub\u003e(d). (e, f)2D asynchronous FTIR patterns between 1600-1750 cm-1 of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e (e) and IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e (f). (g, h)1D SAXS curves during stretching and 2D SAXS patterns (inner photos) from original samples to stretching samples of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e (g) and IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e (h). (i-l)DMA curves of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e (i), HDI-mAr\u003csub\u003e1000\u003c/sub\u003e (j), IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e (k) and IPDI-mAr\u003csub\u003e1000\u003c/sub\u003e (l) with temperature variation. Peaks of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e’s loss tangent curve and the plateau area of its storage modulus curve are particularly noted in the figure.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-6802660/v1/f06c940bad7e92660255a1a5.png"},{"id":84764088,"identity":"1932b877-8b5b-40ba-ae14-d024d4dfeb25","added_by":"auto","created_at":"2025-06-17 06:46:36","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":2327182,"visible":true,"origin":"","legend":"\u003cp\u003e(a)Five types of hard segments involved in the \u003cem\u003eab initio\u003c/em\u003e calculation and their corresponding molecular structures. (b)The HDI-pAr (\u003cem\u003ecis\u003c/em\u003e) dimer structure after geometric optimization, with the main hydrogen bonds and their lengths indicated by dashed lines (the core structure is bolded for clear display). (c)The energy changes after the formation of dimers for the hard segment molecules containing HDI-related structures. Only the energy values that contribute positively to the formation of the dimers are presented. (d)Schematic representation of the dispersion energy contributions from each atom within the dimers of HDI-pAr (\u003cem\u003ecis\u003c/em\u003e) (upper) and HDI-mAr (lower). Atoms shown in red contribute more to the dispersion binding energy. (e)Schematic representation of the weak interactions within the dimers of HDI-pAr (\u003cem\u003ecis\u003c/em\u003e) (upper) and HDI-mAr (lower). The areas represented by different colors correspond to specific interactions as indicated in the legend\u003csup\u003e [59]\u003c/sup\u003e. Notably, the HDI-pAr (\u003cem\u003ecis\u003c/em\u003e) dimer exhibits distinct van der Waals interaction bands, indicating the presence of pronounced π-π stacking interactions. (f)Energy changes (solvent dissociation energy) of the five dimers in different solvent environments. Lower solvent dissociation energy means that the dimers are less likely to dissolve in the corresponding solvent.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-6802660/v1/b959d4c9a2695ae34392e79e.png"},{"id":84764101,"identity":"af52a853-877a-4b3d-989a-36c2eae43a7b","added_by":"auto","created_at":"2025-06-17 06:46:37","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":18186133,"visible":true,"origin":"","legend":"\u003cp\u003e(a)Engineering stress-strain curves of HZPU series, measured at the stretching speed of 50 mm/min. (b)Photograph showing the HDI-pAr\u003csub\u003e1000\u003c/sub\u003e tensile strips can be stretched up to 100 mm without breaking (original length = 10 mm). (c)Photograph showing an HDI-pAr\u003csub\u003e1000\u003c/sub\u003e strip which only weights 0.1 g can smoothly lift a 5 kg load. (d)Photograph showing the shapes that return after stretching up to 400% of four HZPU samples. The top of the photo shows the unstretched original strip, with the distance between the two dashed lines measuring 10 mm. Beside the original strip, the remaining strips correspond to the four samples arranged from top to bottom, respectively. The stretching deformation recovery rate calculated for each sample is labeled on the right side of each strip, while the specific calculation method can be found in the supporting information. (e)Comparison of the tensile strength and toughness between the best one (HDI-pAr\u003csub\u003e1000\u003c/sub\u003e) in HZPU samples prepared in our study and existing representative reported works or commercial products. Materials that enhance performance through the use of multiple interactions, as well as materials with structures similar to HZPU series, have been specially highlighted. The numbers above all data points correspond to the reference citation for each material. (f)Comparison of the tensile strength between the best one (HDI-pAr\u003csub\u003e1000\u003c/sub\u003e) in HZPU samples prepared in our study and existing representative reported ultra-high-strength elastomers, which are classified based on the component score (types of raw materials used in the preparation process). The numbers above all data bars correspond to the reference citation for each material, while the subscript a and b under the same citation number denote two different samples from the same reference. (g)Cyclic loading-unloading tensile curves at 500% strain with different recovery conditions of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e. (h)The normalized stress-relaxation curves of HDI-pAr\u003csub\u003e1000 \u003c/sub\u003eat different temperatures. (i)Relaxation time-temperature Arrhenius fit of HZPU series. (j)Stress-strain SHPB curves of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e at different strain rates. Inner: Maximum stress of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e at different strain rates.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-6802660/v1/d73d49a137dc1e97fa7ac5aa.png"},{"id":84764091,"identity":"391b50cf-40a3-4d67-8673-48d1ae9388e2","added_by":"auto","created_at":"2025-06-17 06:46:36","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":1725224,"visible":true,"origin":"","legend":"\u003cp\u003e(a)Engineering stress-strain curves of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e under different temperatures. Inner: photograph which illustrates HDI-pAr\u003csub\u003e1000\u003c/sub\u003e can still be stretched up to 1000% at 100°C. (b)Engineering stress-strain curves between original HDI-pAr\u003csub\u003e1000\u003c/sub\u003e and reformed (using the hot-pressing method) samples. Inner: The complete cyclic secondary forming (hot pressing) process. (c)Engineering stress-strain curves of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e under different chemical situations for 9 hours, respectively. Inner: photograph showing the macroscopic shape changes of different HZPU series samples after being immersed in a 1 mol/L sodium hydroxide solution for 9 hours and then thoroughly dried. The uppermost strip represents the original shape. The four strips, excluding the original one, correspond to HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, HDI-mAr\u003csub\u003e1000\u003c/sub\u003e, IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e, and IPDI-mAr\u003csub\u003e1000\u003c/sub\u003e samples, respectively. As shown, HDI-pAr\u003csub\u003e1000 \u003c/sub\u003elargely retains its original shape with only slight warping. In contrast, the other strips exhibit significant shape changes, especially the IPDI series, which fragmented during the drying process, preventing the measurement of its mechanical properties. (d)Engineering stress-strain curves of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e after being soaked in different types of solvents and then dried completely. Inner: photographs showing the distinct performances of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e and HDI-mAr\u003csub\u003e1000\u003c/sub\u003e in DMF, under room temperature. (e)Summary of the performance advantages and application prospects of the perfect HZPU materials we have developed. (f)Photographs showing the circuit encapsulated in the HDI-pAr\u003csub\u003e1000\u003c/sub\u003e coating, consisting of complex conductive copper foil paths and a central red LED light. Even under large-angle bending, the LED light remains stable and functions normally. (g)Photograph illustrating the encapsulated circuit completely immersed in the high-salinity simulated seawater solution for three days. During this time, the circuit continues to function stably without any signs of water ingress or corrosion. (h)Photographs showing bio-inspired pneumatic fingers made from HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, installed on a mechanically operated system controlled by airflow. When the airflow is introduced through the pipeline into the system, the pneumatic finger closes, allowing it to grasp objects. The greater the airflow, the stronger the gripping force. The photo below displays the fine structure of a single pneumatic finger, with grooves on its surface created by hot pressing in a specific mold, designed to facilitate the gripping of objects more effectively. (i)Photographs showing pneumatic fingers used to grasp a fragile block of tofu and release it intact without any damage. (j)Photographs showing pneumatic fingers used to grasp a 500g iron weight and maintain it in a suspended state in dichloromethane (left photo) and a 15% hydrochloric acid solution (right photo).\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-6802660/v1/003635d653c92ef50be29119.png"},{"id":91183482,"identity":"27d0ca12-2e80-4dfc-bf4a-ec5474a87a30","added_by":"auto","created_at":"2025-09-12 13:29:01","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":29728277,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6802660/v1/748eea6f-d066-4f7a-be93-579593a8c636.pdf"},{"id":84764093,"identity":"b4f8284c-2e8c-4a79-a405-6fb29f99e49e","added_by":"auto","created_at":"2025-06-17 06:46:37","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":9141803,"visible":true,"origin":"","legend":"Supporting Information: Ultra-Strong and Highly-Robust Elastomers with Synergistic Multiple Weak Interactions","description":"","filename":"SupportInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-6802660/v1/c4dcdb6aa719d96b3cf0cfe2.docx"},{"id":84764086,"identity":"9117b6e5-9385-4e83-a6df-90d03f069943","added_by":"auto","created_at":"2025-06-17 06:46:36","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":319639,"visible":true,"origin":"","legend":"","description":"","filename":"TableofContent.docx","url":"https://assets-eu.researchsquare.com/files/rs-6802660/v1/a945b3dc6d1329f23aa8839e.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Ultra-Strong and Highly-Robust Elastomers with Synergistic Multiple Weak Interactions","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eDue to their excellent toughness, ductility, and exceptional strength, polymeric elastomers have found extensive application prospects in various advanced fields such as the automotive and aerospace industries, soft robotics, and flexible wearable devices \u003csup\u003e[\u003cspan additionalcitationids=\"CR2 CR3\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]\u003c/sup\u003e. Understanding the influence of internal structures on the macroscopic properties of elastomers, and thereby achieving superior overall performance, has long been a momentous challenge. Although numerous specialty elastomers with high strength have been reported \u003csup\u003e[\u003cspan additionalcitationids=\"CR6 CR7\" citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]\u003c/sup\u003e, unfortunately, these materials often rely on complex molecular designs and intricate synthesis strategies, which hinders the real-world applications of these high-performance elastomers. At the same time, besides enhancing macroscopic mechanical properties of these elastomers such as tensile strength and toughness at room temperature, there has been increasing demands for strong resistance to high temperatures, organic solvents, and chemicals \u003csup\u003e[\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]\u003c/sup\u003e. However, achieving a balance between excellent mechanical properties and specialized performance in a single material often requires the use of complicated composite techniques to meet practical requirements \u003csup\u003e[\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]\u003c/sup\u003e. It is undisputable that solving these dilemmas requires a deeper understanding of the microstructure and uncovering the essential logical connections between material structures and performance.\u003c/p\u003e \u003cp\u003eNature provides an abundance of remarkably intricate and inspiring structural templates. The imitation and enhancement of various natural elastomeric structures have been extensively reported, such as modifying polymer chain topologies to mimic the structure and mechanical properties of biological elastic tissues \u003csup\u003e[\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]\u003c/sup\u003e and replicating the microphase-separated structure of spider silk for the development of artificial textile materials \u003csup\u003e[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]\u003c/sup\u003e. These examples of high-performance elastomers have demonstrated that emulating the structural features of natural materials, particularly by implementing soft-hard phase separation within a material, is an effective strategy. This approach enables different regions of the material to respond hierarchically to external stimuli, allowing the material to accommodate large-scale macroscopic deformations. In detail, the strength and toughness of elastomers are simultaneously dependent on their ability to rapidly dissipate external energy and the robustness of their local structures. For instance, in a multilayered soft-hard segregated phase structure, the tightly packed hard domains can withstand high stresses and restrict molecular chain slippage, while the soft domains efficiently distribute and transfer stress to the hard domains, preventing excessive localized stress concentration. As a result, this hierarchical phase separation increases the degree of phase separation by improving the strength and density of the hard segment stacking, which is considered to be a key factor in enhancing overall mechanical performances \u003csup\u003e[\u003cspan additionalcitationids=\"CR16\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eBased on this concept, materials capable of spontaneous phase aggregation and separation due to unique intermolecular interactions have attracted significant interest for their exceptional performance. For example, polyurethane (PU) is a representative biomimetic polymer system with a highly tunable molecular architecture and strong intermolecular interactions. The presence of multiple hydrogen bonds and other complex weak interactions within PU allows for the self-assembly of soft and hard segments, forming phase-separated microscopic structures similar to those found in biological elastomers. This distinctive architecture endows PU with outstanding macroscopic mechanical properties \u003csup\u003e[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIn the development of high-performance elastomers, represented by PU, adjusting the chemical structure of the molecular chains to further enhance intermolecular interactions and improve mechanical performance has also become a common strategy \u003csup\u003e[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]\u003c/sup\u003e. However, achieving elastomers with ultra-high strength (e.g., tensile strength exceeding 100 MPa) and comprehensive properties still remains highly challenging, which typically requires the introduction of complex functional groups, structural blending, or cumbersome post-processing techniques to increase the molecular interactions, such as hydrogen bonding, thereby enhancing hard segment stacking. In addition, the understanding of the relationship between multiscale structures and performance is still limited, leading to a lack of effective structural design methods. Based on this premise, we propose a novel strategy to significantly enhance the overall material performance through precise optimization of the molecular chain structure, complemented by accurate theoretical calculations. We argue that, rather than simply increasing the types and quantity of weak interactions in the material, synergistically combining different weak interactions is a more efficient approach, which necessitates fine-tuning specific structures to facilitate the arrangement and stacking of the hard segments. Therefore, we should not only adjust critical structural parameters, including the distribution of hydrogen bonds, the selection of phenyl ring substitution positions, and chain segment flexibility, but also specifically screen and calculate the intermolecular interactions of the different-positioned phenyl ring structures within the hard segments. Innovative and precise quantum chemical calculations were further integrated to validate our viewpoint, providing a comprehensive and intuitive explanation of the structure-property relationship and the origin of the exceptional performance. These results strongly support the efficacy of our precise molecular chain control strategy. It is particularly noteworthy that, unlike the traditional strategy of increasing the complexity of the backbone to enhance weak interaction density in high-performance elastomer synthesis, our approach focuses on a deeper understanding of the microscopic structural arrangement of the segments.\u003c/p\u003e \u003cp\u003eIn this work, we designed a kind of special PU synthesized from common and inexpensive feedstocks: PTMEG, HDI or IPDI, and phthalic dihydrazide (PDHZ), with the latter two as the core building blocks to construct the hard segment framework of the material. Thus, a variety of nitrogen-hydrogen groups, oxygen-hydrogen groups, and large-area π-π conjugated structures with diverse chemical environments were introduced. This enables the simultaneous localization of various hydrogen bonds and π-π stacking interactions. Additionally, the relative positional relationship between the dihydrazide group and the phenyl ring can be easily fine-tuned, facilitating the study of the effects of structural changes on the promotion of multiple weak interactions and general properties, thus validating our hypothesis. By applying refined structural modifications at the molecular level, we synthesized a series of ultra-strong, high-performance hydrazide-based polyurethanes (HZPU) with highly symmetric hard segment structures using a simple process and a minimal set of commercially available raw materials (only three primary components), achieving a remarkable enhancement in performance compared to structurally similar conventional materials. Via \u003cem\u003eab initio\u003c/em\u003e DFT simulation, we observed hydrogen bond arrangement driven by the localization effect of the π-π stacking of phenyl rings. Unlike traditional high-strength materials that enhance the types and density of hydrogen bonds by introducing complicated hard segment structure, this work focuses more on the combination and synergistic promotion of various weak interactions, thereby improving the efficiency of spontaneous formation of hydrogen bonds. The synthesized representative material exhibits unprecedented mechanical properties, achieving an ultrahigh tensile strength of approximately 104.7 MPa, an elongation at break of ~\u0026thinsp;1000%, and exceptional toughness of ~\u0026thinsp;460.5 MJ/m\u0026sup2;. Further investigations confirm that the hierarchical hard segment stacking within the material endows the material with prominent mechanical strength, superior thermal resistance, outstanding relaxation resistance, and remarkable durability under various harsh chemical environments. These attributes significantly enhance and expand its multifunctionality and potential applications. This work not only introduces a novel and remarkable paradigm for elastomer research but also represents a significant step forward in the exploration and optimization of high-performance material systems.\u003c/p\u003e"},{"header":"2. Results and Discussion","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Synthesis and Structural Characterization of HZPU Series\u003c/h2\u003e \u003cp\u003eInitially, hydroxyl-terminated polytetramethylene ether glycols (PTMEG) whose number-average molecular weights (\u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e) equal to 1,000 were selected to form the soft segments. These were then reacted in precise molar ratios with two widely used commercial isocyanates\u0026mdash;hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI)\u0026mdash;to produce two types of prepolymers. Notably, HDI introduces flexible six-carbon alkyl chains into the product molecules, while IPDI incorporates bulky six-membered cyclohexane rings. Following this, two kinds of different dihydrazides (terephthalic dihydrazide (p-PDHZ) and isophthalic dihydrazide (m-PDHZ)) were used as chain extenders to further polymerize the prepolymers into HZPU macromolecules. Although these two dihydrazides share the same chemical formula, their functional group substitution patterns differ, leading to variations in the conformations of the hard segment chains in the products. Ultimately, products synthesized from HDI and p-PDHZ were successfully obtained and labeled as HDI-pAr\u003csub\u003e1000\u003c/sub\u003e. Additionally, samples HDI-mAr\u003csub\u003e1000\u003c/sub\u003e, IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e, and IPDI-mAr\u003csub\u003e1000\u003c/sub\u003e and other similar products were obtained, collectively forming the HZPU series, in order to enable a detailed comparison of the practical performance of products with different hydrazide substitution positions, and distinct diisocyanate compositions. The most optimal sample was subsequently selected for further analysis, with the overall process illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, while the specific synthesis methods, along with additional information and the rest samples, are provided in the supporting information. For HZPU, the incorporation of urea structural units, formed via the reaction between hydrazide groups and isocyanates, provides a robust basis for the formation of diverse, high-density, localized hydrogen-bond clusters \u003csup\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]\u003c/sup\u003e. As demonstrated in the following parts, under optimal structural configurations, highly symmetric hydrogen-bond networks were generated, correlating with the prominent macroscopic properties of the resulting samples. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb clearly demonstrated the overall microscopic structure of the HZPU samples.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFour samples (HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, HDI-mAr\u003csub\u003e1000\u003c/sub\u003e, IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e, and IPDI-mAr\u003csub\u003e1000\u003c/sub\u003e) were analyzed using Fourier-transform infrared spectroscopy (FTIR) to identify and compare hydrogen bonding interactions. The spectral region between 1600 and 1750 cm⁻\u0026sup1; was deconvoluted into seven distinct peaks. Specifically, the peaks at 1725 cm⁻\u0026sup1; (Peak I) and 1690 cm⁻\u0026sup1; (Peak III) correspond to free urethane and urea carbonyl vibrations, respectively. Peaks at 1710 cm⁻\u0026sup1; (Peak II) and 1670 cm⁻\u0026sup1; (Peak IV) are attributed to urethane and urea carbonyls involved in random, disordered hydrogen bonds, while the remaining peaks represent carbonyl groups forming ordered hydrogen bond clusters \u003csup\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u003c/sup\u003e. Integration of the peak areas revealed that the sample derived from HDI and p-PDHZ (HDI-pAr\u003csub\u003e1000\u003c/sub\u003e) exhibited the highest proportion of hydrogen-bonded carbonyl groups, up to 73.62%. Among these, about 51.56% were associated with ordered hydrogen-bonded carbonyls, clearly surpassing the other samples (49.19%, 47.79% and 48.49% for HDI-mAr\u003csub\u003e1000\u003c/sub\u003e/HDI-mAr\u003csub\u003e1000\u003c/sub\u003e/HDI-mAr\u003csub\u003e1000\u003c/sub\u003e, respectively, refer to Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea-b and \u003cb\u003eFigure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e-2\u003c/b\u003e). These findings indicate that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e contains a dense network of ordered hydrogen bonds, suggesting a more regular hard-segment structure. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec-f and \u003cb\u003eFigure S3\u003c/b\u003e further illustrate the FTIR spectra of the four samples under varying temperatures, along with the corresponding synchronous and asynchronous two-dimensional (2D) infrared spectra. Using Noda\u0026rsquo;s 2D IR correlation theory \u003csup\u003e[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]\u003c/sup\u003e, it is demonstrated that for HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, the relative proportion of disordered hydrogen bonds and amorphous carbonyls to ordered hydrogen bonds remained stable as the temperature increased. This highlights that the internal hydrogen-bonding network of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e is robust and retains stability over a certain temperature range. In contrast, the other samples exhibit significant transitions in carbonyl groups with rising temperatures, shifting from ordered hydrogen-bonded urethane and urea carbonyls to disordered or free carbonyls, alluding to inferior hydrogen bond stability, with noticeable breakdowns or conversions occurring due to temperature changes. In summary, FTIR results preliminarily signify that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e possesses a dense and highly stable hydrogen-bonding network, suggesting the presence of a high-strength and localized hard-segment structure.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo further elucidate the differences in phase structures among the prepared samples, small-angle X-ray scattering (SAXS) measurements were conducted on the samples in both their pristine and stretched states, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eg-h and \u003cb\u003eFigure S4-5\u003c/b\u003e. Based on the physical relationship between the peak position \u0026#119902; of the scattering signal and the corresponding size \u0026#119889; of the aggregated regions \u003csup\u003e[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]\u003c/sup\u003e, given by the formula:\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:\\begin{array}{c}d=\\frac{2\\pi\\:}{q}\\#2-1\\end{array}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eFollowing this, the estimated dimensions of the stacked hard segment regions in different HZPU samples were determined. For HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, the scattering peak position q is observed at 0.083 \u0026Aring;\u003csup\u003e\u0026minus;1\u003c/sup\u003e, corresponding to an average dimension of the aggregated hard segment regions (represented as the mean inter-segmental spacing) of approximately 7.57 nm. This value is notably larger than that of other samples, such as IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e, where the calculated hard segment dimension is 5.11 nm. This suggests that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e forms a more extensive hard segment domain. Additionally, the scattering peak intensity of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e is relatively higher, and its two-dimensional SAXS pattern in the original state exhibits apparently more pronounced scattering features compared to other samples. This indicates that the hard segment regions in HDI-pAr\u003csub\u003e1000\u003c/sub\u003e not only span a larger area but also exhibit greater structural regularity and a higher hydrogen bond density. At the initial stage of the tensile process, the scattering peak of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e shifts further to the left while maintaining a high peak intensity. This reveals that during stretching, the molecular chains undergo alignment, and the hard segment stacking regions continuously undergo orientation while retaining strong resistance to tensile stress, resulting in further expansion of the scattering area size. Only under extreme stretching do the hard domains begin to break down. In contrast, for the other samples, the scattering peak intensity decreases noticeably even at the early stages of stretching, suggesting that their hard domains have relatively weaker resistance to tensile stress, with significant disruption occurring early in the stretching process. SAXS results obtained under tensile strain demonstrate that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e maintains a high density and structurally regular extensive hard segment domain over a range of strain levels, underscoring its remarkable stability and responsiveness.\u003c/p\u003e \u003cp\u003eDynamic mechanical analysis (DMA) experiments (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ei-l) further confirm that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e exhibits multiple distinct transition points: A single peak observed at -59.5\u0026deg;C corresponds to the glass transition temperature (\u003cem\u003eT\u003c/em\u003e\u003csub\u003e\u003cem\u003eg\u003c/em\u003e\u003c/sub\u003e) of the soft segments within the molecular chains. In addition, a more complex peak shape appears in the temperature range above 100\u0026deg;C, corresponding to the motion of the hard segments. Notable peaks appear at 112.3\u0026deg;C and 161.6\u0026deg;C, indicating cascaded responses in the hard segment interactions within the sample near these temperature points. In comparison, the other samples exhibit a clear decline in the storage modulus with increasing temperature, lacking a stable modulus plateau, and show a vague loss tangent peak at high temperatures. This suggests that, compared to HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, the hard segment interactions in the other samples are weaker, leading to higher mobility and activity with increasing temperature, which adversely affects the macroscopic mechanical properties. Furthermore, at temperatures exceeding 200\u0026deg;C, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e maintains a storage modulus of over 10 MPa and preserves a stable macroscopic form, demonstrating thermal resistance even comparable to that of thermosetting polymers with chemical crosslinking structures. In contrast, the other samples completely soften and flow below 175\u0026deg;C. In conclusion, compared to the other samples, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e possesses a higher glass transition temperature of its hard segments and superior thermal resistance, highlighting the presence of robust and stable hard domains.\u003c/p\u003e \u003cp\u003eAll these characterizations mentioned above suggest that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, compared to other formulations, is likely to possess superior mechanical and physical properties. To investigate the underlying structural distinctions responsible for the formation of its high-performance hard segment regions, more detailed theoretical simulations are analyzed and discussed in subsequent sections.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Structural Theoretical Calculation and Simulation of HZPU Series\u003c/h2\u003e \u003cp\u003eThe characterization results of the HZPU series samples clearly demonstrate that HDI-pAr1000 possesses an exceptionally stable hard domains, sparking curiosity and interest in exploring the differences in the aggregated structures of various HZPU molecular chains. Computational chemistry and simulation serve as powerful tools for uncovering structures and behaviors at a fundamental molecular level and have been widely employed in the analysis of various materials in previous studies. Unfortunately, there is still a lack of a systematic and convincing comprehensive analysis process for polymer systems, especially PU, due to the complex and dense interactions within the system. Additionally, the high molecular weight and the diversity of functional groups limit the precision of computational simulations. Currently, common simulation approaches involve using coarse-graining (CG) methods to simplify the molecular chain structure, expecting to strike a balance between accuracy and computational time, or employing empirical molecular dynamics methods to roughly calculate macroscopic thermodynamic quantities for specific molecular chain conformation \u003csup\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]\u003c/sup\u003e. However, the former approach inevitably overlooks certain fine interactions when simplifying the structure, particularly with regard to the arrangement and strength of various hydrogen bonds in elastomers, which cannot be precisely predicted. In the latter approach, the specific molecular chain conformations often need to be subjectively assigned, which may not reflect the actual configurations of the molecular chains within the system, while empirical molecular dynamics methods always limit the accuracy of the simulations as well. A more systematic and rigorous scheme would be preferred to conduct extensive conformational searches and first-principles calculations on elastomer molecular chains at a high precision level, but this is prohibitively expensive.\u003c/p\u003e \u003cp\u003eTo address these issues, we adopt a more efficient method for theoretical calculations and behavior predictions for HZPU. We propose that, as previously mentioned, the dominant interactions within HZPU should be multi-hydrogen bonding and π-π stacking, primarily provided by the conjugated benzene ring system and highly electronegative atoms in the hard segment of the molecular chain. Therefore, the macroscopic performance and characteristics of the system are strongly correlated with the changes in the internal hard segment structure. Consequently, extracting and simulating the hard segment part of the molecular chain in depth, rather than performing direct calculations on the entire molecular chain, can innovatively reflect the influence of the HZPU molecular structure on its performance to a large extent, all within a limited and acceptable computational time frame. Hence, in our theoretical calculation work, the hard segment regions of the four samples were individually extracted, while the connected soft segment regions were replaced with methyl groups. Among them, the molecular structure formed by the reaction of p-PDHZ with HDI was further classified into two models with different symmetries (\u003cem\u003ecis\u003c/em\u003e and \u003cem\u003etrans\u003c/em\u003e) based on the orientation of the carbonyl groups attached to the benzene ring. This classification was carried out to precisely study the subtle differences in the molecular structure and their impact on the hard segment interactions. It should be noted that the HDI-pAr\u003csub\u003e1000\u003c/sub\u003e material obtained through actual synthesis is an isomeric mixture containing both \u003cem\u003ecis\u003c/em\u003e and \u003cem\u003etrans\u003c/em\u003e molecular structures. Following this approach, five distinct molecules of hard segments were obtained: three models formed with HDI as the monomer, each consisting of 84 atoms, and two molecules formed with IPDI as the monomer, each consisting of 104 atoms. All the structures are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea. With the aid of density functional theory (DFT), renowned for its high precision and accuracy, \u003cem\u003eab initio\u003c/em\u003e methods were employed to conduct a detailed analysis of the five molecules.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe entire computational work was performed using the xtb software \u003csup\u003e[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]\u003c/sup\u003e and Gaussian 16 Version A.03 \u003csup\u003e[\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]\u003c/sup\u003e, with detailed steps provided in the supporting information. Firstly, the five molecules were optimized after a large-scale and comprehensive conformational searching process, and single-point energy calculations were performed on the optimized structures. In the following text, the five molecules are denoted as \u003cb\u003eI\u003c/b\u003e to \u003cb\u003eV\u003c/b\u003e, corresponding to the hard segment of HDI-pAr\u003csub\u003en\u003c/sub\u003e (\u003cem\u003ecis\u003c/em\u003e), HDI-pAr\u003csub\u003en\u003c/sub\u003e (\u003cem\u003etrans\u003c/em\u003e), HDI-mAr\u003csub\u003en\u003c/sub\u003e, IPDI-pAr\u003csub\u003en\u003c/sub\u003e and IPDI-mAr\u003csub\u003en\u003c/sub\u003e, respectively, with their specific structures shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea. Based on this, structural optimizations were carried out for the dimers of the five molecules, leading to the lowest-energy dimer configurations and the corresponding dimer interaction energies. The results show that the interaction energy of molecule \u003cb\u003eI\u003c/b\u003e is -72.65 kcal/mol, which is significantly stronger than that of the other molecules. From the optimized structure, it can be observed that the \u003cem\u003ecis\u003c/em\u003e-terephthalic dihydrazide and HDI combination enables the hard segments to form a prominent π-π stacking interaction as well as various types of hydrogen bonding. The benzene rings involved in the π-π stacking interaction play a good localization role, promoting the formation of a multi-type hydrogen bond network, which expedites effective packing of the hard segments and enhances their performance. In detail, when the \u003cem\u003ecis\u003c/em\u003e-configured HDI-pAr hard segments stack in an alternating orientation, the planar π orbitals formed by the benzene rings and amide groups achieve effective overlap. This overlap strengthens the interaction between hard segments and organizes the spatial configuration of urea and carbamate groups, restricting them within appropriate regions. As a result, the formation of ordered hydrogen bonds is greatly facilitated, increasing the density of weak interactions between atoms and yielding a symmetrically centered and refined structure, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb. In contrast, molecule \u003cb\u003eII\u003c/b\u003e, based on \u003cem\u003etrans\u003c/em\u003e-terephthalic dihydrazide, does not form the optimal structure mentioned above. This is because the molecular structure causes the planar π orbitals formed by the amide and benzene rings to twist when both interactions are simultaneously formed, leading to an increase in energy. Compared to the molecules based on HDI, molecules \u003cb\u003eIV\u003c/b\u003e and \u003cb\u003eV\u003c/b\u003e, due to the steric hindrance introduced by the six-membered ring of IPDI, also have difficulty in forming a structure similar to molecule \u003cb\u003eI\u003c/b\u003e. Therefore, based on the theoretical calculations, it is revealed that the use of terephthalic dihydrazide and HDI as polymerization monomers leads to samples (HDI-pAr\u003csub\u003en\u003c/sub\u003e) with ordered packing of hard segments due to the \u003cem\u003ecis\u003c/em\u003e-terephthalic dihydrazide units, resulting in performance improvements distinct from those of ordinary HZPU series. Consequently, it is expected that HDI-pAr\u003csub\u003en\u003c/sub\u003e will exhibit exceptional comprehensive performance.\u003c/p\u003e \u003cp\u003eNext, an energy decomposition based on dispersion-corrected DFT methods \u003csup\u003e[\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]\u003c/sup\u003e was performed for the five dimer configurations. Specifically, the interaction energy of the dimers was decomposed into the following energy components:\u003cdiv id=\"Equb\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equb\" name=\"EquationSource\"\u003e\n$$\\:\\begin{array}{c}{\\varDelta\\:E}_{int}={\\varDelta\\:E}_{e}+{\\varDelta\\:E}_{ex-rp}+{\\varDelta\\:E}_{o}+{\\varDelta\\:E}_{d}\\#2-2\\end{array}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eAmong them, \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sub\u003e and \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003eo\u003c/em\u003e\u003c/sub\u003e represent the electrostatic interaction energy and the orbital interaction energy between the dimers, respectively, and \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sub\u003e represents the dispersion-corrected energy. \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003eex\u0026minus;rp\u003c/em\u003e\u003c/sub\u003e describes the DFT functional-related corrections and repulsive effects between the dimers, which negatively affect the energy lowering during dimer interaction. In the polyurethane system, multiple hydrogen bonds are weak interactions primarily driven by electrostatic forces, while π-π interactions are considered as dispersion interactions. Therefore, the value of \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sub\u003e can partially reflect the hydrogen bonding density in the five dimers, while \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sub\u003e can measure the strength of the π-π interactions within the dimer. All computational results are presented in the Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec and \u003cb\u003eFigure S6\u003c/b\u003e. It can be observed that the dimer of molecule \u003cb\u003eI\u003c/b\u003e indeed exhibits relatively strong dispersion interactions, indicating good π-π stacking, which contributes to the structural regularization of the dimer and further enhances the density of multiple hydrogen bonds (compared to the other molecules, \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sub\u003e decreased by approximately 14 kcal/mol). Comparing the dimers of molecules \u003cb\u003eIV\u003c/b\u003e and \u003cb\u003eV\u003c/b\u003e containing IPDI components, it is noted that although the dimer formed by molecule \u003cb\u003eIV\u003c/b\u003e also shows strong dispersion interactions, these interactions primarily arise from the overlapping of bulky carbon rings in the molecule rather than π-π stacking. As a result, the influence on the overall structure of the hard segment is smaller, and the enhancement in multiple hydrogen bond density is not significant (compared to molecule \u003cb\u003eV\u003c/b\u003e, \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sub\u003e decreased by approximately 7 kcal/mol). The energy decomposition results show that, in structures with a similar number of hydrogen bonding sites and configurations (e.g., molecules \u003cb\u003eI\u003c/b\u003e, \u003cb\u003eII\u003c/b\u003e, and \u003cb\u003eIII\u003c/b\u003e), the actual number and strength of hydrogen bonds (represented by \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sub\u003e) are positively correlated with \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sub\u003e, which mainly represent the contribution of π-π stacking. The \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sub\u003e and \u003cem\u003e∆E\u003c/em\u003e\u003csub\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sub\u003e values for molecule \u003cb\u003eI\u003c/b\u003e are higher than those of all other dimers, providing in-depth evidence that HDI-pAr\u003csub\u003en\u003c/sub\u003e (\u003cem\u003ecis\u003c/em\u003e) simultaneously exhibits π-π stacking interactions and multiple hydrogen bonding, with the former promoting the formation of the latter. Specifically, due to the strong π-π stacking effect, the hard segments can spontaneously recognize and assemble. Simultaneously, as the π-π stacking is formed, the polar groups and hydrogen atoms on both sides of the phenyl rings in the hard segment also reach appropriate spatial positions. As a result, compared to similar elastomer systems that only contain hydrogen bonds or lack the ability to form hydrogen bonds together with π-π stacking, the formation of multiple hydrogen bonds becomes much easier and more efficient, particularly when the material undergoes dynamic behavior and spontaneous recovery. This effect allows our material to achieve high density of hydrogen bonds and hard segment stacking, which is beneficial for macroscopic performance. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed-e clearly visualizes the considerable weak interactions and the dispersion energy contributions from individual atoms within the dimer of molecule \u003cb\u003eI\u003c/b\u003e. In contrast, the visualizations of all other dimers can be found in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed-e and \u003cb\u003eFigure S7-14\u003c/b\u003e.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eThe \u003cem\u003eab initio\u003c/em\u003e calculation results for the dimer energies of the five hard segment molecules.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHDI-pAr\u003csub\u003en\u003c/sub\u003e (\u003cem\u003ecis\u003c/em\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHDI-pAr\u003csub\u003en\u003c/sub\u003e(\u003cem\u003etrans\u003c/em\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eHDI-mAr\u003csub\u003en\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eIPDI-pAr\u003csub\u003en\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eIPDI-mAr\u003csub\u003en\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTotal Dimer Binding Energy (kcal/mol)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-90.52\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-76.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-81.71\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-87.87\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-84.21\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e∆E\u003c/b\u003e\u003csub\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sub\u003e \u003cb\u003e(kcal/mol)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-114.76\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-99.86\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-100.38\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-111.87\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-104.59\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e∆E\u003c/b\u003e\u003csub\u003e\u003cb\u003eex\u0026minus;rp\u003c/b\u003e\u003c/sub\u003e \u003cb\u003e(kcal/mol)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e160.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e171.71\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e124.31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e171.81\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e129.48\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e∆E\u003c/b\u003e\u003csub\u003e\u003cb\u003eo\u003c/b\u003e\u003c/sub\u003e \u003cb\u003e(kcal/mol)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-50.38\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-43.65\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-42.64\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-47.26\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-45.95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e∆E\u003c/b\u003e\u003csub\u003e\u003cb\u003ed\u003c/b\u003e\u003c/sub\u003e \u003cb\u003e(kcal/mol)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-85.42\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-74.55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-63.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-100.54\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-63.15\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eAdditionally, previous work highlights that in polymeric elastomers with spontaneous soft and hard segment separation, well-stacked hard segment regions often endow the corresponding materials with remarkable robustness and solvent resistance \u003csup\u003e[\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]\u003c/sup\u003e. Inspired by this, we conducted simulations to analyze the dissolution performance of the five dimers in various solvents, further elucidating the performance differences within the HZPU elastomer series and their potential for specialized applications. Therefore, an implicit solvent model (SMB) \u003csup\u003e[\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]\u003c/sup\u003e was applied to calculate the total energy reduction values of the five dimers in different solvent environments, in order to assess the effect of different hard segment compositions on the solubility performance of the samples. Three representative solvents (dimethylformamide (DMF), tetrahydrofuran (THF), and dichloromethane (DCM)) were used in the calculations, with the results shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef. According to the results, the dimer formed by molecule \u003cb\u003eI\u003c/b\u003e possesses the relatively lowest energy reduction in all three solvents, indicating that the hard segment region of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e (\u003cem\u003ecis\u003c/em\u003e) has the strongest resistance to dissolution in these solvents. This further reveals the stacking strength of the hard segments and provides theoretical support for the sample's excellent solvent endurance.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Mechanical Properties Evaluation of HZPU Series\u003c/h2\u003e \u003cp\u003eThe physical characterization tests of the HZPU series mentioned earlier reveal that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e possesses a unique and novel robust hard segment stacking structure, while detailed theoretical calculations further support that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, based on its distinctive hard segment chemical structure, can spontaneously form an attractive highly-symmetric cluster network, endowing it with extraordinary macroscopic mechanical properties. To verify our hypothesis, we conducted a series of diverse mechanical performance tests on the HZPU series samples. Tensile experiments were performed on the four representative samples with varying hard segment structures (HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, HDI-mAr\u003csub\u003e1000\u003c/sub\u003e, IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e, and IPDI-mAr\u003csub\u003e1000\u003c/sub\u003e), as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea. Among the samples, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e exhibits extraordinary mechanical properties, with maximum engineering tensile stress reaching 104.7 MPa, elongation-at-break of 1000% (ten times the original sample length, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb), and toughness up to 460.51 MJ/m\u0026sup3;. Its true stress exceeds 1 GPa, far surpassing the performance of the other samples and aligning well with the results from structural characterization and quantum mechanical simulations. The tensile curves also reveal that, despite the only structural difference between HDI-pAr\u003csub\u003e1000\u003c/sub\u003e and HDI-mAr\u003csub\u003e1000\u003c/sub\u003e being the substitution position on the benzene ring within the hard segments, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e demonstrates significantly superior mechanical properties and distinct tensile curve. In contrast, the tensile curves of IPDI-pAr\u003csub\u003e1000\u003c/sub\u003e and IPDI-mAr\u003csub\u003e1000\u003c/sub\u003e nearly overlap, indicating similar mechanical performance. This suggests that the benzene ring substitution position has negligible influence on the properties of HZPU prepared with IPDI, whereas the unique and highly regular hard segment structures within HDI-pAr\u003csub\u003e1000\u003c/sub\u003e strongly enhance its macroscopic performance.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec, under natural conditions, an HDI-pAr\u003csub\u003e1000\u003c/sub\u003e strip sample weighing only about 0.1g can stably hang weights larger than 5 kg (equivalent to 50,000 times its own weight) without fracture, demonstrating truly remarkable mechanical properties. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed further illustrates the elastic recovery of the HZPU series samples. After stretching all the HZPU strips to 400% of their original length and allowing sufficient time for natural recovery, all samples return to a length close to their original state. Among them, the HZPU samples prepared with HDI show a more complete recovery, indicating that the long alkyl chain structure in HDI provides more freedom for molecular chain movement compared to IPDI, resulting in superior recovery performance. Compared with previous comprehensive studies on high-performance non-heterocyclic PU elastomers, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, which owns an extremely simple structure and does not require a complicated preparation process, possesses the highest mechanical strength known to date astonishingly \u003csup\u003e[\u003cspan additionalcitationids=\"CR35 CR36 CR37 CR38 CR39 CR40 CR41 CR42 CR43 CR44 CR45 CR46\" citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e]\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee). It not only surpasses various crosslinked adaptive network (ANs)-based elastomers that rely on multiple weak interactions but also outperforms ultra-strong spider silk and other bioinspired high-performance materials with similar architectures. Notably, studies using materials and structures closely resembling those in our samples are highlighted in the figure for direct comparison. By finely tuning the specific chemical structures within the hard segments, we successfully achieve a substantial performance improvement over these existing reports and provide a detailed theoretical explanation of the underlying mechanisms. This strongly validates the feasibility and potential of precision structural adjustments in polymer elastomers. Furthermore, compared to many high-performance elastomer manufacturing methods, the raw materials and fabrication processes for HZPU are relatively simple, further augmenting its scalability and adaptability for broader applications. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ef, the component score is defined as the number of types of raw materials required to prepare the corresponding material (excluding catalysts and solvents, only counting the reactants that form the main molecular structure of the material). When compared to several recently reported representative ultra-high-strength elastomers (not limited to PU-based materials), HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, with a component score of only 3 and an extremely straightforward preparation process, demonstrates mechanical performance comparable to the best-known elastomers with component score equal to 4. It can also rival the performance of more complex elastomers with component score equal to 5 or more, while significantly outperforming other high-performance materials with the same component score (3). This achieves a perfect balance between preparation complexity and apparent performance, setting a new record for constructing ultra-strong elastomer using an uncomplicated approach.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFurther mechanical tests were conducted to comprehensively evaluate the in-depth properties of the HZPU samples. Figures\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg and Figure \u003cb\u003eS19-21\u003c/b\u003e display the results of cyclic tensile experiments. HDI-pAr\u003csub\u003e1000\u003c/sub\u003e and other samples were stretched to 500% strain at a rate of 50 mm/min, then returned to their original length at the same rate. After allowing the samples to naturally recover at different times and temperatures during the stretching process, a secondary tensile test was performed to assess the samples' rebound capacity and stability. The tests revealed that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e achieved an exceptionally high energy loss value, reaching 54.8 MJ/m\u0026sup3;, as represented by the hysteresis loop formed by the return curve, which reflected the material's extraordinary energy dissipation ability. Meanwhile, after a short period of rest, the stretched HDI-pAr\u003csub\u003e1000\u003c/sub\u003e strip was able to recover most of its performance. Notably, when placed in a 70\u0026deg;C oven for just 5 minutes, the energy loss modulus recovered to 48.6 MJ/m\u0026sup3; (88.7% of the original value). Moreover, the tensile stress corresponding to the maximum strain (500%) showed no significant change, demonstrating that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e not only possesses powerful stress dissipation capabilities but also exhibits excellent rebound and damage recovery abilities. This makes it a highly reliable fatigue-resistant elastomer, owing to the ease with which the hydrogen bond network, enhanced by the positioning effect of the benzene rings, spontaneously assembles reversibly under stretching conditions.\u003c/p\u003e \u003cp\u003eSince the hard segment stacking in HZPU primarily relies on weak interactions, such as multiple hydrogen bonds and π-π stacking, the physical crosslinking within the material is characterized by variable and reversible properties. This allows for continuous stretching at different temperatures, enabling the observation of the material's relaxation behavior and providing a means to assess the stability of the physical crosslinking within the hard segments. The relaxation time (τ) for all samples is defined as the time required for the internal stress to decrease to 1/e of the initial tensile stress, from which the corresponding relaxation activation energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e) is calculated using the Kohlrausch-Williams-Watts relaxation theory and the Arrhenius equation \u003csup\u003e[\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e]\u003c/sup\u003e. Basically, higher absolute value of relaxation activation energy indicates stronger stacking and crosslinking of the hard segments, as well as better thermal stability. Detailed experimental results are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eh-i and Figure \u003cb\u003eS16-18\u003c/b\u003e. HDI-pAr\u003csub\u003e1000\u003c/sub\u003e exhibits a strikingly high relaxation activation energy (131.62 kJ/mol), which even far exceeds that of many dynamic covalently crosslinked elastomers based on chemical bonding that have been previously reported \u003csup\u003e[\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e]\u003c/sup\u003e, demonstrating the exceptional hard segment cluster structure within HDI-pAr\u003csub\u003e1000\u003c/sub\u003e provides a level of physical crosslinking that rivals the strength of chemical bonding. Moreover, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e was unable to reach the corresponding relaxation level within a limited time at 75\u0026deg;C, while further extrapolation using the Arrhenius equation suggests that its theoretical relaxation time at room temperature (25\u0026deg;C) reaches an astonishing 1.4\u0026times;10⁹ seconds, equivalent to approximately 45 years, highlighting its excellent high-temperature resistance and anti-relaxation properties, which aligns with our expectations. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ej further show the results of the HDI-pAr\u003csub\u003e1000\u003c/sub\u003e sample in the split-Hopkinson pressure bar test. As the strain rate of the dynamic load increases over an ultra-short period, the maximum stress rises significantly. At a high strain rate of 5000 s⁻\u0026sup1;, the peak stress reaches up to 320 MPa, with the overall stress level much higher than that of various elastomeric materials previously reported \u003csup\u003e[\u003cspan additionalcitationids=\"CR63\" citationid=\"CR62\" class=\"CitationRef\"\u003e62\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e]\u003c/sup\u003e. This illustrates that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e exhibits exceptional impact resistance, with the ability to rapidly dissipate stress in a short period, showcasing strong local resistance to failure. In summary, the results of all the mechanical experiments demonstrate that the HZPU series, particularly HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, possesses outstanding and comprehensive mechanical properties, impressively surpassing numbers of conventional elastomers. These results further denote the accuracy of theoretical simulations and physical structural characterization, confirming the success of the precise polymer structural control strategy.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Performance of Optimal HDI-pAr\u003csub\u003e1000\u003c/sub\u003e under Various Harsh Environments and Derived Applications\u003c/h2\u003e \u003cp\u003eAttributable to its highly stable and extensive hard segment domains, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e exhibits not only extraordinary macroscopic mechanical properties but also remarkable stability under conditions that are exceedingly challenging for conventional thermoplastic elastomers. Specifically, tensile tests were performed on the samples at various temperatures, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea. The results reveal a gradual decline in maximum engineering stress with increasing temperature, which is a predictable outcome stemming from enhanced molecular chain mobility. Nevertheless, even after thermal equilibration at 100\u0026deg;C, the material maintains a relatively high tensile stress (~\u0026thinsp;51.4 MPa) and a wide strain range. It is worth noting that among many widely applied or reported high-performance elastomers mentioned earlier, a considerable number fails to achieve tensile strengths exceeding 50 MPa under ambient conditions. This suggests that even at elevated temperatures, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e maintains mechanical properties that rival or even surpass those of similar materials, underscoring its exceptional potential for high-temperature applications. Interestingly, the tensile test results at 75\u0026deg;C and 100\u0026deg;C are nearly identical, indicating that HDI-pAr\u003csub\u003e1000\u003c/sub\u003e possesses a tiered temperature response, with significant loosening of the hard segments occurring only beyond 100\u0026deg;C. The results from the previous DMA tests also confirm this observation: in the temperature-dependent DMA data for HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, the second loss tangent peak at 112.3\u0026deg;C suggests that the hard segment regions within the material begin to undergo a transition at this temperature, which lies higher than 100\u0026deg;C. Additional experiments, presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb, involved reprocessing crushed HDI-pAr\u003csub\u003e1000\u003c/sub\u003e samples at elevated temperatures (\u0026gt;\u0026thinsp;160\u0026deg;C). The reprocessed samples exhibited no notable changes in macroscopic appearance, transparency, or mechanical properties, demonstrating that the hard segment structures can reorganize efficiently without compromising performance. These findings highlight the exceptional recyclability of HZPU at high temperatures, significantly expanding its application scenarios.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe results of the aforementioned theoretical simulations not only confirmed the presence of highly distinctive and orderly hard segment clusters within HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, but also predicted its resistance to dissolution using an implicit solvent model. This was further validated through a series of experiments. Compared to other samples in the HZPU series, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e also demonstrates outstanding chemical durability and solvent resistance, allowing for its application as a high-performance material in extreme environments. Figures\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec and \u003cb\u003eFigure S\u003c/b\u003e22-28 present the performance variations of four HZPU samples after exposure to strong acidic, alkaline, and high-concentration saline solutions. The samples were immersed in 1 mol/L hydrochloric acid, 1 mol/L sodium hydroxide, and 2 mol/L sodium chloride solutions for up to 9 hours. Afterward, they were retrieved, thoroughly dried, and weighed to evaluate mass loss before tensile testing. The results indicate that all samples maintained excellent resistance to acid and saline treatments. However, when subjected to alkaline conditions, all samples except HDI-pAr\u003csub\u003e1000\u003c/sub\u003e underwent severe degradation, with some failing to retain a recoverable shape. This outcome aligns with the well-known catalytic effect of bases in accelerating the hydrolysis of polyurethane materials. In contrast, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e showed minimal deformation in post-treatment, retaining its structural integrity with only slight warping and minor mass loss. Furthermore, its mechanical strength and elongation at break remained near pre-treatment levels, emphasizing its robustness under harsh chemical conditions. A similar trend emerged when organic solvents were introduced (Figs.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed and \u003cb\u003eFigure S\u003c/b\u003e29). Tests utilized three representative solvents: tetrahydrofuran (THF), dichloromethane (DCM), and dimethylformamide (DMF), also partially correspond to theoretical simulations. HDI-pAr\u003csub\u003e1000\u003c/sub\u003e was immersed in these solvents for three days before drying. Impressively, the material retained stability across all three solvents. Even when exposed to elevated temperatures in DMF, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e preserved its mechanical properties over a prolonged period (3 hours) with only slight reductions. The shredded HDI-pAr\u003csub\u003e1000\u003c/sub\u003e was further immersed in DMF for up to thirty days, during which it still did not dissolve, only experiencing slight swelling. By contrast, other HZPU samples dissolved entirely in DMF at room temperature within just one hour. The unparalleled structural strength and chemical resistance of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e\u0026rsquo;s hard segments have been firmly validated through these experiments.\u003c/p\u003e \u003cp\u003eGiven the excellent special properties of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, we believe it can be applied in a variety of important scenarios where high-performance novel materials are required (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee). These include utilizing its anti-relaxation and high stability properties for construction raw materials or long-term biomedical implants; leveraging its excellent thermal resistance for high-temperature sensors or specialized thermal insulation linings; exploiting its exceptional mechanical strength for aerospace materials or high-performance biomimetic grippers; and taking advantage of its outstanding chemical resistance for manufacturing anti-corrosion devices or protective inner linings for transport pipelines, among others. For example, HDI-pAr\u003csub\u003e1000\u003c/sub\u003e can be used as an excellent circuit encapsulation material. After encapsulation, the circuit with a complex shape can withstand significant bending while maintaining stable performance (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ef). This is due to the high toughness and strong energy dissipation ability of the HZPU material. When the encapsulated circuit is bent and immersed in simulated seawater (a 2 mol/L mixed solution of sodium chloride and magnesium chloride, with the actual electrolyte concentration much higher than that of real seawater), the encapsulation material\u0026rsquo;s excellent resistance to saline solutions allows the circuit to remain stable and conductive for over three days without any signs of corrosion (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eg). Another very interesting and practically significant example is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eh, leveraging the material's inherent advantages of easy processing, re-molding without performance loss. A special-shaped pneumatic finger was designed and easily manufactured. This device can regulate its opening and closing states, as well as the force of closure, by controlling the airflow entering it. In practical use, thanks to the high toughness and elasticity of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, the pneumatic finger can precisely grasp and release fragile block-shaped tofu (a kind of common Chinese soft food product), without any damage to the tofu after gripping and releasing, as seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ei. Additionally, for heavier objects, such as a 500g weight, the pneumatic finger can easily lift them up and maintain the position for a long time in extreme conditions, including 15% hydrochloric acid solution or dichloromethane, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ej. All behaviors are highly similar to human fingers, with even greater stability and resistance to harsh conditions. In summary, these applications not only demonstrate the versatility and simplicity of using HZPU in various special environments but also further validate and showcase their ultra-high strength, diverse special properties, and remarkable resistance to harsh environmental conditions. These findings reveal the potential of the material as a candidate solution for addressing numerous practical challenges, shedding light on the long-standing issue of the lack of suitable, high-performance elastomeric materials for such applications.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Conclusion","content":"\u003cp\u003eIn contrast to the previous approaches typically increasing weak interaction sites between molecular chains by incorporating complicate local chemical structures, in this work we propose an innovative strategy via fine-tuning and optimizing local chemical structures to cooperatively promote various weak interactions, such as π-π stacking and multiple hydrogen bonds. The phenyl ring units substituted with hydrazide groups were chosen as the core structural component due to their abundant hydrogen bonding sites, localized and stackable strong π orbital effects, and excellent tunability of local structures and symmetry. Comprehensive quantum chemical calculations based on DFT theory were innovatively applied to thoroughly investigate and compare the interactions within the hard segments of the material. The results reveal that, in the \u003cem\u003ecis\u003c/em\u003e hard segment of HDI-pAr\u003csub\u003e1000\u003c/sub\u003e, symmetric molecular structures allow for the local molecular chains to adopt configurations that facilitate long-range ordering and the simultaneous formation of multiple weak interactions. The benzene ring-dominated π-π stacking serves as an anchoring and positioning mechanism, thereby facilitating the efficient and spontaneous formation of multiple hydrogen bonds, thereby resulting in efficient energy dissipation and extraordinary properties. Consequently, the obtained elastomer exhibits unparalleled tensile strength (104.7 MPa) and toughness (460.5 MJ/m\u0026sup3;), along with excellent performance in various aspects, such as thermal resistance (tensile strength above 50 MPa at 100\u0026deg;C), strong elastic recovery (88.7% recovery of the energy loss modulus after 5 minutes at 70\u0026deg;C), and anti-relaxation properties (relaxation activation energy of 131.62 kJ/mol, with a relaxation time of 45 years at room temperature). Further experiments confirmed that the elastomer also demonstrates remarkable resistance to extreme chemical conditions, such as strong acid, strong base, concentrated salt solutions, and various organic solvents, paving the way for its potential use as a high-performance specialty elastomer in extreme environments. In conclusion, through the synthesis of the unparalleled high-performance HZPU material and a series of solid theoretical analyses, our strategy of precise microstructure optimization of polymer elastomers combined with computational chemistry for mechanistic explanation and prediction has proven to be both innovative and effective. This approach provides a directional guidance for studying and exploiting the complex interactions within polymers. It is particularly noteworthy that, by logically combining theoretical simulation calculations with experiments according to the method employed in this work, the associations and synergistic effects of different interactions can be clearly evaluated and adjusted, thus accelerating the development of high-performance materials. We believe that the findings from this work have significant implications for the further creation of high-performance polymer materials and have also prompted a simulation-guiding-experiments paradigm for discovering new materials.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eSupporting Information\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSupporting\u0026nbsp;information is available\u0026nbsp;from the Wiley Online Library or from the author.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;Acknowledgements\u003c/p\u003e\n\u003cp\u003eThis work is supported by the National Natural Science Foundation of China (No. 52403011).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eJ. M. Lehn, \u003cem\u003eAngew. Chem. Int. Ed. Engl.\u003c/em\u003e 1998, \u003cem\u003e27\u003c/em\u003e, 89\u0026ndash;112.\u003c/li\u003e\n\u003cli\u003eE. J. Markvicka, M. D. Bartlett, X. Huang, C. Majidi, \u003cem\u003eNat. 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Gong, \u003cem\u003eMatter\u003c/em\u003e \u003cstrong\u003e2022\u003c/strong\u003e, \u003cem\u003e5\u003c/em\u003e, 2265.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"elastomer, polyurethane, hard domains, ab initio computation, weak interactions","lastPublishedDoi":"10.21203/rs.3.rs-6802660/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6802660/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe increasing demand for high-performance elastomers has spurred research aimed at enhancing comprehensive properties. However, challenges such as complex molecular structures and poor understanding of structure-property relationship have hindered the development of advanced elastomers. To address these limitations, we propose a strategy that strengthens the intermolecular interactions via synergistic multiple weak interactions and leverages theoretical calculations. Adoption of symmetric hard segments effectively organizes π-π stacking, which have a positioning effect and lead to an increase in the spontaneous formation efficiency of multiple hydrogen bonds, resulting in ordered hard domains. Thereby, polyurethane elastomers with exceptional properties were successfully developed by using simple and efficient processes, achieving tensile strength of 104.7 MPa and toughness of 460.5 MJ/m\u0026sup3;, which surpass substantial numbers of existing materials. These also exhibit superior resilience, thermal, and chemical resistance, as well as anti-relaxation behavior, making them ideal for extreme conditions. Additionally, we employed rigorous \u003cem\u003eab initio\u003c/em\u003e calculations to analyze the structure of specific segments, which convincingly demonstrate the immense impact of even slight changes of molecular structure and segment arrangement on material performance and provide excellent predictive power for material properties. Consequently, this work establishes a novel framework with vast potential for advancing innovation in high-performance materials.\u003c/p\u003e","manuscriptTitle":"Ultra-Strong and Highly-Robust Elastomers with Synergistic Multiple Weak Interactions","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-17 06:46:31","doi":"10.21203/rs.3.rs-6802660/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"0c7e8ee4-4703-4588-a6d0-1fece7f4f8c1","owner":[],"postedDate":"June 17th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":50106935,"name":"Physical sciences/Materials science/Structural materials/Mechanical properties"},{"id":50106936,"name":"Physical sciences/Chemistry/Chemical engineering"},{"id":50106937,"name":"Physical sciences/Materials science/Soft materials/Polymers"},{"id":50106938,"name":"Physical sciences/Materials science/Theory and computation/Atomistic models"},{"id":50106939,"name":"Physical sciences/Materials science/Soft materials/Organic molecules in materials science"}],"tags":[],"updatedAt":"2025-09-12T13:20:38+00:00","versionOfRecord":[],"versionCreatedAt":"2025-06-17 06:46:31","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6802660","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6802660","identity":"rs-6802660","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}