An adhesive material with reversible stretch-universal adhesion and its preparation method and application

Abstract

The application belongs to the field of liquid adhesive materials, and specifically comprises an adhesive material with reversible stretchability and universal adhesion, and a preparation method and application thereof. The preparation method of the adhesive material comprises the following steps: S1, mixing deionized water and acidic polyose with a weight average molecular weight of 0.8-2 MDa, stirring to dissolve, and obtaining an acidic polyose solution; S2, adding an inorganic metal salt to the acidic polyose solution, stirring to dissolve, and obtaining a precursor solution; S3, adding concentrated hydrochloric acid to the precursor solution, stirring to thicken the system, standing, and self-assembling to obtain the adhesive material. The addition amount of the concentrated hydrochloric acid is 0.1-0.325 wt% of the mass of the deionized water. The adhesive material prepared by the above method has high energy dissipation efficiency and an ultra-long reversible stretchability, can effectively withstand the transient impact load brought by a high-speed moving target, and provides stable adhesion, and is suitable for stable adhesion on various complex structure surfaces.

Description

Technical Field

[0001] This invention belongs to the field of liquid adhesive materials, specifically including an adhesive material with reversible stretch universal adhesion, its preparation method and application. Background Technology

[0002] With the widespread application of low-altitude unmanned systems and artificial intelligence equipment technologies in the maritime and air domains, the demand for highly reliable and low-loss capture and recovery of moving targets is increasing. Especially in missions such as maritime search and rescue and aerial drone recovery, how to achieve stable adhesion in complex environments (such as large deformation impact, fluid disturbance, and multiphase interface switching) has become a key focus of current soft matter materials science research.

[0003] Current capture and adhesion docking technologies are mainly divided into mechanical and chemical adhesion. Traditional mechanical claws or mesh capture devices often cause severe damage to the target surface due to rigid contact when facing high-speed moving targets, and are difficult to adapt to targets with irregular shapes. Chemical adhesion, as a flexible capture and connection method, has received widespread attention in recent years. It achieves capture / connection through the wetting of polymer segments at the interface and covalent / non-covalent interactions. Currently, commercial / industrial grade liquid adhesion materials (such as cyanoacrylate, epoxy resin, etc.) are often designed as highly cross-linked rigid structures to achieve high-strength adhesion. However, these materials lack effective molecular breakage-reorganization and energy dissipation mechanisms, resulting in significant brittleness when subjected to sudden external impacts, and are prone to stress concentration leading to deadhesion. At the same time, when facing complex fluid environments, most liquid adhesion materials are prone to phase separation or physical adhesion failure due to interfacial energy mismatch, such as when facing low surface energy or highly wetted surfaces like oil and water, and cannot establish effective connections at oil-contaminated or water-wetted interfaces. In addition, traditional adhesive materials are mostly irreversibly cured and do not have reversibility under ultra-large deformation. When dealing with the need for large-scale target swing or repeated capture, the fatigue failure of the material seriously affects the capture success rate.

[0004] Therefore, it is necessary to design a viscoelastic adhesive material with high energy dissipation capacity, wide interfacial adaptability and extreme environmental tolerance to meet the technical requirements of "multi-morphological non-destructive capture" and "cross-media stable adhesion" in modern complex dynamic environments. Summary of the Invention

[0005] In view of the problems existing in the prior art, the first objective of this invention is to provide a method for preparing an adhesive material with reversible stretch universal adhesion. The preparation process of the reversible stretch universal adhesion adhesive material of this invention is simple, the raw materials are widely available and relatively inexpensive, and it is easy to prepare and apply on a large scale in industrial applications, thus possessing extremely high industrialization potential.

[0006] A second objective of this invention is to provide an adhesive material with reversible, universally applicable tensile adhesion, prepared using the method described above. This adhesive material can undergo a maximum ductile deformation of 90,000%, and achieves reversible rebound within this deformation range. Furthermore, it can adhere to solid surfaces with contact angles ranging from 3 to 157°, and also achieves relatively strong adhesion to water or oil surfaces. Moreover, by controlling the composition of the raw materials, the viscosity of this adhesive material can be adjusted within a wide range of 10 to 1000 Pa·s, enabling wetting, spreading, and robust adhesion on various complex surface structures.

[0007] A third objective of this invention is to provide an adhesive material with reversible, stretchable, universal adhesion.

[0008] A fourth object of the present invention is to provide an adhesion device.

[0009] To achieve the first objective mentioned above, the technical solution adopted by the present invention includes:

[0010] This invention discloses a method for preparing an adhesive material with reversible stretch universal adhesion, comprising the following steps:

[0011] S1, deionized water and weight-average molecular weight (M) w Acidic polysaccharides with a concentration of 0.8–2 MDa were mixed and stirred until dissolved to obtain an acidic polysaccharide solution.

[0012] S2. Add the inorganic metal salt to the above acidic polysaccharide solution and stir until dissolved to obtain the precursor solution;

[0013] S3. Add concentrated hydrochloric acid to the precursor solution, stir until the system becomes viscous, let it stand, and self-assemble to obtain an adhesive material with reversible stretching universal adhesion.

[0014] In the adhesive material protected by this invention, a three-dimensional dynamic network with an efficient energy dissipation mechanism based on non-dynamic covalent interactions is constructed through the interaction of acidic polysaccharides, inorganic metal salts, and concentrated hydrochloric acid. Under external tensile force, the dynamic non-covalent bonds undergo programmed "fracture and recombination," suppressing stress concentration through the dissipation mechanism. Furthermore, thanks to the self-healing properties of the dynamic non-covalent bonds, the adhesive material exhibits no significant degradation in adhesion and mechanical properties after undergoing stretching and shrinking of several times its length, greatly improving the reusability of the capture system.

[0015] Furthermore, the addition of concentrated hydrochloric acid introduces a large number of hydrogen ions into the system, which facilitates the formation of double hydrogen bonds with the carboxyl groups in the acidic polysaccharide, thereby enhancing the density of the three-dimensional dynamic network of the adhesive material. This dense dynamic network is not rigid but possesses extremely high degrees of sliding freedom. During extreme stretching, the dynamic exchange mechanism of double hydrogen bonds allows the molecular chains to be highly oriented along the stretching direction and form an ordered fiber bundle structure. When the external force is removed, the hydrogen ion-mediated hydrogen bonding drives the network to rapidly retract to its initial state, achieving complete reversibility of the material under ultra-large deformation. In one specific embodiment, the amount of concentrated hydrochloric acid added is 0.1–0.325 wt% of the mass of deionized water; exemplarily, the amount of concentrated hydrochloric acid added is 0.1 wt%, 0.125 wt%, 0.15 wt%, 0.175 wt%, 0.2 wt%, 0.225 wt%, 0.25 wt%, 0.275 wt%, 0.3 wt%, 0.325 wt%, etc., of the mass of deionized water. If too much concentrated hydrochloric acid is added, the cohesion of the adhesive material system will be too high, resulting in a non-adhesive solid that cannot deform over a large area. Conversely, if too little concentrated hydrochloric acid is added, the viscosity of the adhesive material system will be too low. After adhering to the target object, even a small deformation will cause capillary breakage of the adhesive material, resulting in capture failure.

[0016] Furthermore, the acidic polysaccharide, as the main material of this system, provides the network framework. It not only possesses abundant adhesion functional groups, enabling it to cope with various complex and extreme adhesion environments (such as high-speed movement, large deformation, oil contamination, and high humidity), establishing strong non-covalent bonds and improving the success rate of adhesion and capture, but also exhibits good biocompatibility, making it suitable for ecologically sensitive environments and the non-destructive capture of biological targets. In one specific embodiment, the acidic polysaccharide is selected from hyaluronic acid (e.g., M...). w ~1.8 MDa), xanthan gum (e.g., M... w ~2 MDa), galvanic gum (e.g., M w ~2 MDa), warming roller adhesive (e.g., M w ~2 MDa), pectin (e.g., M w ~1.5 MDa), sodium alginate (e.g., M... w ~1 MDa), carrageenan (e.g., M w ~1MDa), fucoidan (e.g., M... w ~0.8 MDa), Ulva polysaccharides (e.g., M... w One or more of (~2 MDa).

[0017] Furthermore, the mass ratio of deionized water to acidic polysaccharide is 1:0.005 to 0.02; for example, the mass ratio of deionized water to acidic polysaccharide can be 1:0.005, 1:0.01, 1:0.015, 1:0.02, etc.

[0018] Furthermore, inorganic metal salts are uniformly distributed within the network framework formed by the acidic polysaccharide through metal coordination, thereby providing physical cross-linking points. In one specific embodiment, the inorganic metal salt is selected from one or more of calcium chloride, magnesium chloride, magnesium sulfate, sodium chloride, zinc chloride, zinc sulfate, potassium chloride, ferrous chloride, ferric chloride, aluminum chloride, and copper chloride.

[0019] Furthermore, the amount of inorganic metal salt added is 0.01 to 0.2 wt% of the mass of deionized water; for example, the amount of inorganic metal salt added is 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.11 wt%, 0.12 wt%, 0.13 wt%, 0.14 wt%, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, 0.2 wt% of the mass of deionized water, etc.

[0020] Furthermore, in step S1, the stirring rate is 1000-1200 rpm, and the stirring time is 1-2 hours.

[0021] Furthermore, in step S2, the stirring rate is 1000-1200 rpm and the stirring time is 10-20 min.

[0022] Furthermore, in step S3, the stirring rate is 1000-1400 rpm and the stirring time is 10-30 min.

[0023] To achieve the second objective mentioned above, the technical solution adopted by the present invention includes:

[0024] This invention discloses an adhesive material with reversible stretching universal adhesion, which is prepared by the preparation method described above. The adhesive material is based on acidic polysaccharide molecular chains as a backbone, and forms a three-dimensional dynamic network structure through non-dynamic covalent interaction.

[0025] Furthermore, the viscosity of the adhesive material ranges from 10 to 1000 Pa·s, the maximum toughness deformation reaches 90000%, and the maximum adhesion strength exceeds 10 kPa (up to 18 kPa).

[0026] To achieve the third objective mentioned above, the technical solution adopted by the present invention includes:

[0027] This invention discloses an adhesive material with reversible stretch universal adhesion. The raw materials for preparing the adhesive material, by weight, include...

[0028] 0.5-2 parts of acidic polysaccharides with a weight-average molecular weight of 0.8-2 MDa;

[0029] Inorganic metal salt, 0.01-0.2 parts;

[0030] 0.1-0.325 parts concentrated hydrochloric acid;

[0031] Water 99.39-97.475 parts;

[0032] The adhesive material is a three-dimensional dynamic network structure formed by the self-assembly of acidic polysaccharide molecular chains as the backbone through non-dynamic covalent interactions.

[0033] Furthermore, the acidic polysaccharide, as the main material of this system, provides the network framework. It not only possesses abundant adhesion functional groups, enabling it to cope with various complex and extreme adhesion environments (such as high-speed movement, large deformation, oil contamination, and high humidity), establishing strong non-covalent bonds and improving the success rate of adhesion and capture, but also exhibits good biocompatibility, making it suitable for ecologically sensitive environments and the non-destructive capture of biological targets. In one specific embodiment, the acidic polysaccharide is selected from hyaluronic acid (e.g., M...). w ~1.8 MDa), xanthan gum (e.g., M... w ~2 MDa), galvanic gum (e.g., M w ~2 MDa), warming roller adhesive (e.g., M w ~2 MDa), pectin (e.g., M w ~1.5 MDa), sodium alginate (e.g., M... w ~1 MDa), carrageenan (e.g., M w ~1MDa), fucoidan (e.g., M... w ~0.8 MDa), Ulva polysaccharides (e.g., M... w One or more of (~2 MDa).

[0034] Furthermore, the inorganic metal salt is selected from one or more of calcium chloride, magnesium chloride, magnesium sulfate, sodium chloride, zinc chloride, zinc sulfate, potassium chloride, ferrous chloride, ferric chloride, aluminum chloride, and copper chloride.

[0035] To achieve the fourth objective mentioned above, the technical solution adopted by the present invention includes:

[0036] The present invention discloses an adhesion device, the adhesion device comprising a substrate and an adhesion material as described above coated on the substrate; exemplaryly, the substrate is a mesh material, more specifically, for example, a woven mesh.

[0037] Beneficial effects of this invention:

[0038] The adhesive material based on a three-dimensional network structure of dynamic "fracture-recombination" of hydrogen bonds possesses high energy dissipation efficiency and ultra-long reversible tensile strength, effectively withstanding transient impact loads from high-speed moving targets and providing stable adhesion. The dynamic polymer network within the adhesive material eliminates stress concentration caused by large deformations, preventing brittle fracture and greatly expanding its application in dynamic capture scenarios. For illegally launched small drones, the adhesive device disclosed in this invention, such as a woven net coated with adhesive material, can capture high-speed moving drones and instantly dissipate their kinetic energy, achieving rapid and low-damage adhesion. Its excellent toughness also effectively prevents the drone from escaping, achieving an "unbreakable" effect. The self-healing properties of the adhesive material can effectively and promptly repair microscopic damage caused by extreme tension or environmental stress, maintaining the integrity of the network structure. Simultaneously, the abundant adhesive functional groups of the acidic polysaccharide can effectively match surfaces with different wettability, allowing the adhesive material to rapidly spread and wet upon contact, thus achieving adhesion. Even on surfaces subjected to extreme conditions such as high humidity or oil contamination, the adhesive material of this invention maintains stable adhesion, significantly enhancing its tolerance to diverse environments. Furthermore, the use of polysaccharides as the primary material imparts excellent biocompatibility, making its applications in biomedical and ecologically sensitive fields safer. This invention achieves a balance between mechanical adhesion and elasticity, and a high degree of unity between interfacial adhesion and environmental universality, through precise adjustment of the strength of molecular-level interactions, demonstrating significant technological advancement and industrial application value. Attached Figure Description

[0039] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0040] Figure 1 This is a schematic diagram illustrating the preparation process and structure of an adhesive material with reversible stretchable universal adhesion.

[0041] Figure 2 Electron micrograph of the reversible stretch universal adhesion adhesive material prepared in Example 1.

[0042] Figure 3 This is a schematic diagram of the curved arrangement structure of the reversible stretch universal adhesion adhesive material prepared in Example 1 after stretching.

[0043] Figure 4 A photograph of the reversible stretching universal adhesion material prepared in Example 1 after reversible stretching.

[0044] Figure 5 Test images of the ultra-long reversible stretch universal adhesion adhesive material prepared in Example 1 on oil / water surfaces and under different wettability conditions.

[0045] Figure 6 The impact resistance test results of the adhesive materials prepared in Example 4 and Comparative Example 2 are compared.

[0046] Figure 7 The image shows the adhesion of a reversible, stretchable, universally adhesive material prepared in Example 5 to capture a drone.

[0047] Figure 8 Electron micrograph and test image of the solid-like gel prepared for Comparative Example 1. Detailed Implementation

[0048] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further clarifies the invention. It should be understood that the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0049] Example 1

[0050] The preparation process is illustrated in Figure 1. The adhesive material with reversible stretchable universal adhesion is prepared according to the following method:

[0051] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.005 and stirred at 1000-1200 rpm at room temperature for 1-2 h to prepare an acidic polysaccharide solution;

[0052] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of calcium chloride added is 0.01 wt% of the mass of deionized water, and stir at 1000-1200 rpm at room temperature for 10-20 min to prepare the precursor solution.

[0053] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.125 wt% of the mass of deionized water. Then, stir rapidly at 1000-1400 rpm for 10-30 min to ensure that the entire system is stirred evenly until the system becomes a viscous, stringy liquid. Let it stand for 10 min to obtain an adhesive material with reversible stretching universal adhesion.

[0054] Figure 2 This is a three-dimensional network structure electron microscope image of the reversible stretch universal adhesion adhesive material prepared in Example 1. Figure 3The image shows an electron microscope (EM) image of the reversible, universally applicable adhesive material after stretching, illustrating its curved arrangement structure. As can be seen from the image, this invention breaks through the physical limitations of static cross-linking in traditional polymer adhesive materials, exhibiting a unique structural evolution mechanism. When subjected to external tensile stress, the dynamic three-dimensional network within the adhesive material does not undergo brittle fracture. Instead, through the "breakage-reorganization" of non-covalent cross-linking points (e.g., hydrogen bonds), the originally disordered polymer segments are highly oriented along the direction of force, transforming from a three-dimensional network into a tightly packed fiber bundle structure. This instantaneous microstructural transformation not only effectively dissipates the work done by external forces but also provides a solid structural support for the material to achieve extraordinary toughness deformation. Further experiments revealed that when an adhesive material with an initial length of 0.1 mm is stretched, it can be reversibly stretched to ~9 cm (see [reference]). Figure 4 Its ductile deformation can reach up to 90,000% of its own length. The core innovation lies in the fact that this stretching, surpassing conventional elastomer adhesive materials, is completely reversible and non-destructive. When the external tensile stress is removed, the highly oriented fiber bundles can quickly retract, spontaneously reorganizing to restore their initial dense three-dimensional network state, effectively overcoming the problem of irreversible rebound that occurs in traditional elastomer adhesive materials after ultra-large deformation. Furthermore, compared to commercially available adhesives that become brittle and easily break or exhibit irreversible stretching, the "ultra-long reversible stretching" characteristic of this invention establishes an irreplaceable advantage in practical applications. In complex dynamic situations such as capturing high-speed moving targets, this material can act like a "high-pressure buffer spring," fully absorbing and buffering the instantaneous impact energy from the target, truly achieving low-loss capture.

[0055] Figure 5 The diagram shows test images of the reversible stretch universal adhesion material prepared in Example 1 adhering to surfaces with different wettability and oil / water surfaces. It can be seen that the adhesion material can achieve universal adhesion from superphilic to superhydrophobic surfaces. When stretched vertically while still wet, the adhesion material can produce an adhesion strength of 3-6 kPa. Furthermore, even in harsher environments, the present invention can still adhere to surfaces with high water content and oil surfaces, producing an adhesion strength as high as 4 kPa. This demonstrates that the adhesion material of the present invention can cope with surfaces of various surface energies and has excellent broad applicability.

[0056] Example 2

[0057] The preparation process is illustrated in Figure 1. The adhesive material with reversible stretchable universal adhesion is prepared according to the following method:

[0058] S1, Deionized water and hyaluronic acid (M w~1.8 MDa) were mixed at a mass ratio of 1:0.01 and stirred at 1000-1200 rpm at room temperature for 1-2 h to prepare an acidic polysaccharide solution;

[0059] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of calcium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000-1200 rpm at room temperature for 10-20 min to prepare the precursor solution.

[0060] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.175 wt% of the mass of deionized water. Then, stir rapidly at 1000-1400 rpm for 10-30 min to ensure that the entire system is stirred evenly until the system becomes a viscous, stringy liquid. Let it stand for 10 min to obtain a universal adhesive material with a maximum toughness deformation of 90,000%.

[0061] Example 3

[0062] The preparation process is illustrated in Figure 1. The adhesive material with reversible stretchable universal adhesion is prepared according to the following method:

[0063] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.015 and stirred at 1000-1200 rpm at room temperature for 1-2 h to prepare an acidic polysaccharide solution;

[0064] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of calcium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000-1200 rpm at room temperature for 10-20 min to prepare the precursor solution.

[0065] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.25 wt% of the mass of deionized water. Then, stir rapidly at 1000-1400 rpm for 10-30 min to ensure uniform stirring of the entire system until the system becomes a viscous, stringy liquid. Let it stand for 10 min to obtain an adhesive material with reversible tensile universal adhesion. It can generate an adhesion strength of more than 10 kPa when stretched vertically while the adhesive material is still wet, ensuring a toughness deformation of more than 50,000%.

[0066] Example 4

[0067] The preparation process is illustrated in Figure 1. The adhesive material with reversible stretchable universal adhesion is prepared according to the following method:

[0068] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.02 and stirred at 1000 rpm at room temperature for 2 h to prepare an acidic polysaccharide solution;

[0069] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of sodium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare the precursor solution.

[0070] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.325 wt% of the mass of deionized water. Then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred evenly until the system becomes a viscous, stringy liquid. Let it stand for 10 min to self-assemble and obtain an adhesive material with reversible stretching universal adhesion.

[0071] Example 5

[0072] The preparation process is illustrated in Figure 1. The adhesive material with reversible stretchable universal adhesion is prepared according to the following method:

[0073] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.02 and stirred at 1000 rpm at room temperature for 2 h to prepare an acidic polysaccharide solution;

[0074] S2. Add magnesium chloride to the acidic polysaccharide solution, wherein the amount of magnesium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare the precursor solution.

[0075] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.325 wt% of the mass of deionized water. Then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred evenly until the system becomes a viscous, stringy liquid. Let it stand for 10 min to self-assemble and obtain an adhesive material with reversible stretching universal adhesion.

[0076] In practical applications, woven nets coated with adhesive material can capture high-speed moving drones and instantly dissipate their kinetic energy, achieving rapid and low-damage adhesion. Simultaneously, their excellent toughness effectively prevents the drone from escaping, achieving an "unbreakable" effect (see [link to relevant documentation]). Figure 7The material's "unbreakable" characteristic is completely different from the one-time plastic breakage of traditional elastic adhesive materials. This is due to the ultra-long reversible stretching brought about by the reversible transformation of the dense three-dimensional dynamic network and fiber bundle structure. During the dynamic process of drone collision or continuous escape, the adhesive material of this invention can undergo ultra-high-rate tough deformation as the drone escapes, like a "high-pressure buffer spring." A more significant advantage is that when the target's kinetic energy is exhausted or the external force weakens, the highly oriented polymer chains can quickly retract and spontaneously recombine to form a three-dimensional network structure. This excellent complete reversibility not only ensures absolute reliability in a single capture process but also endows the adhesive material with excellent fatigue resistance. Furthermore, after target capture, the adhesive material on the captured target surface can be easily removed by wiping with alcohol, truly achieving low-loss capture from anti-buffering to easy-to-remove. In addition, in actual outdoor airspace operations, the drone surface is often accompanied by rainwater, high humidity, or oil contamination. The adhesive material of this invention, with its unique interfacial wetting ability, can disregard the dryness or wetness of the target surface and material differences (such as metals, Teflon, etc.), rapidly spreading and wetting the surface upon contact to establish a strong molecular-level anchor. This broad-spectrum cross-medium adhesion innovation perfectly compensates for the fatal flaw of traditional interceptor nets that are prone to "slippage" when facing smooth or wet targets, ensuring a high capture success rate in complex dynamic environments.

[0077] Example 6

[0078] The preparation process is illustrated in Figure 1. The adhesive material with reversible stretchable universal adhesion is prepared according to the following method:

[0079] S1. Deionized water and hyaluronic acid (1 MDa) <M w <1.8 MDa) were mixed at a mass ratio of 1:0.015 and stirred at 1000 rpm at room temperature for 1 h to prepare an acidic polysaccharide solution;

[0080] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of calcium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare the precursor solution.

[0081] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.325 wt% of the mass of deionized water. Then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred uniformly until the system becomes a viscous, stringy liquid. Let it stand for 10 min to obtain an adhesive material with reversible stretching universal adhesion.

[0082] Example 7

[0083] The preparation process is illustrated in Figure 1. The adhesive material with reversible stretchable universal adhesion is prepared according to the following method:

[0084] S1. Deionized water and pectin (M w ~1.5 MDa) were mixed at a mass ratio of 1:0.01 and stirred at 1000 rpm at room temperature for 1 h to prepare an acidic polysaccharide solution;

[0085] S2. Add calcium chloride to the acidic polysaccharide solution, the amount of calcium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare the precursor solution.

[0086] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.30 wt% of the mass of deionized water. Then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred uniformly until the system becomes a viscous, stringy liquid. Let it stand for 10 min to obtain a reversible, stretchable, universally adhesive material through self-assembly.

[0087] Comparative Example 1

[0088] The preparation method of the adhesive material includes the following steps:

[0089] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.01 and stirred at 1000 rpm at room temperature for 1.5 h to prepare an acidic polysaccharide solution;

[0090] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of calcium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare the precursor solution.

[0091] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.5 wt% of the mass of deionized water, and then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred uniformly until the system becomes a gel-like solid. Let it stand for 10 min to obtain a dense film structure adhesive material, which is characterized by non-adhesion and inability to achieve large deformation.

[0092] When excessive concentrated hydrochloric acid is introduced, the excess hydrogen ions cause the originally dynamic double hydrogen bonds to transform into high-density packing. This leads to a change in inter-chain interactions from dynamic "point-to-point" crosslinking to strong "face-to-face" locking, thereby driving the chain segments to come close together and undergo physical curling and tight entanglement. This highly coordinated aggregation behavior causes the system to collapse from a three-dimensional network structure into a dense aggregated state, as shown in... Figure 8 The dense film structure is shown. Tests on the material's reversibility revealed that, due to the cohesive force of the adhesive material being much greater than the surface bonding force, it quickly detaches from the substrate during stretching, making large-scale reversible deformation impossible.

[0093] Comparative Example 2

[0094] The preparation method of the adhesive material includes the following steps:

[0095] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.01 and stirred at 1000 rpm at room temperature for 1.5 h to prepare an acidic polysaccharide solution;

[0096] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of calcium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare the precursor solution.

[0097] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.025 wt% of the mass of deionized water, and then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred uniformly. Let stand for 10 min to obtain an adhesive material with a viscosity of less than 1 Pa·s and no elasticity through self-assembly.

[0098] When too little concentrated hydrochloric acid is introduced, the insufficient amount of hydrogen ions causes only a portion of the dissociated carboxylate ions to protonate into carboxylic acids. This results in a limited number of double hydrogen bonds forming between chains, meaning too few crosslinking points for dynamic "breakage-recombination." Consequently, the macroscopic system exhibits low viscosity and inelastic behavior.

[0099] The adhesive materials prepared in Example 4 and Comparative Example 2 were tested as follows:

[0100] A 7 g steel ball was dropped from a height of 52 cm and impacted a 2 cm thick adhesive material sample. The adhesive material prepared in Example 4 effectively dissipated the energy of the initial impact of the high-speed moving target using its viscoelasticity, and firmly adhered to the target, preventing it from bouncing (see Example 4). Figure 6In contrast, in Comparative Example 2, when a high-speed moving target makes its first impact, it lacks sufficient viscoelasticity to dissipate the impact energy and cannot quickly stick to the target, causing the target to bounce repeatedly and eventually detach from the adhesive material, thus failing to capture it.

[0101] Comparative Example 3

[0102] The preparation method of the adhesive material includes the following steps:

[0103] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.01 and stirred at 1000 rpm at room temperature for 1.5 h to prepare an acidic polysaccharide solution;

[0104] S2. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.015 wt% of the mass of deionized water, and then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred uniformly. Let stand for 10 min to obtain a low-toughness deformation adhesive material through self-assembly.

[0105] The absence of inorganic metal ions prevents the protonated carboxylate ions from coordinating. This reduces the number of crosslinking points for dynamic "fracture-reorganization" in the system, leading to capillary fractures in the bulk phase of the macroscopic adhesive material during significant ductile deformation, thus hindering its efficient capture of the target analyte.

[0106] Comparative Example 4

[0107] The preparation method of the adhesive material includes the following steps:

[0108] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.01 and stirred at 1000 rpm at room temperature for 1.5 h to prepare an acidic polysaccharide solution;

[0109] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of calcium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare the precursor solution.

[0110] S3. Add glacial acetic acid to the precursor solution, wherein the amount of glacial acetic acid added is 0.15 wt% of the mass of deionized water. Then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred uniformly. Let stand for 10 min to self-assemble and obtain an adhesive material with a viscosity of less than 1 Pa·s and no elasticity.

[0111] Glacial acetic acid is a weak acid and cannot provide enough hydrogen ions to protonate the carboxylate groups in the system, thus failing to generate dynamic "breakage-recombination" crosslinking points between chains.

[0112] Comparative Example 5

[0113] The preparation method of the adhesive material includes the following steps:

[0114] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.01 and stirred at 1000 rpm at room temperature for 1.5 h to prepare an acidic polysaccharide solution;

[0115] S2. Add calcium chloride to the acidic polysaccharide solution, wherein the amount of calcium chloride added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare the precursor solution.

[0116] S3. Add sulfuric acid to the precursor solution, wherein the amount of sulfuric acid added is 0.15 wt% of the mass of deionized water, and then stir rapidly at 1400 rpm for 20 min to ensure uniform stirring of the entire system. Let stand for 10 min to obtain an adhesive material with a viscosity of less than 1 Pa·s and no elasticity through self-assembly.

[0117] Sulfuric acid has dehydrating properties, leading to the degradation of polysaccharides, and divalent sulfate ions can alter the helical structure of polysaccharides.

[0118] Comparative Example 6

[0119] The preparation method of the adhesive material includes the following steps:

[0120] S1, Deionized water and hyaluronic acid (M w ~1.8 MDa) were mixed at a mass ratio of 1:0.01 and stirred at 1000 rpm at room temperature for 1.5 h to prepare an acidic polysaccharide solution;

[0121] S2. Add silica nanoparticles rich in -OH to the acidic polysaccharide solution, wherein the amount of nanoparticles added is 0.015 wt% of the mass of deionized water, and stir at 1000 rpm at room temperature for 10 min to prepare a precursor solution.

[0122] S3. Add concentrated hydrochloric acid to the precursor solution, wherein the amount of concentrated hydrochloric acid added is 0.15 wt% of the mass of deionized water, and then stir rapidly at 1400 rpm for 20 min to ensure that the entire system is stirred uniformly. Let stand for 10 min to self-assemble and obtain an adhesive material with a viscosity of less than 1 Pa·s and no elasticity.

[0123] Nanoparticles cannot be completely and uniformly dispersed in a system with a certain viscosity, and the interaction between nanoparticles and polysaccharides at the interface is affected by factors such as steric hindrance and mismatch of interaction points, which prevents the generation of sufficient dynamic "fracture-recombination" crosslinking points.

[0124] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is impossible to exhaustively list all possible implementations here. All embodiments falling under the scope of the present invention...

[0125] Obvious variations or modifications derived from the technical solution are still within the scope of protection of this invention.

Claims

1. A method for preparing an adhesive material with reversible stretch universal adhesion, characterized in that, Includes the following steps: S1. Mix deionized water and acidic polysaccharide with a weight-average molecular weight of 0.8-2 MDa, and stir until dissolved to obtain an acidic polysaccharide solution; S2. Add the inorganic metal salt to the above acidic polysaccharide solution and stir until dissolved to obtain the precursor solution; S3. Add concentrated hydrochloric acid to the precursor solution, stir until the system becomes viscous, let stand, and self-assemble to obtain an adhesive material with reversible stretching universal adhesion. The amount of concentrated hydrochloric acid added is 0.1 to 0.325 wt% of the mass of deionized water. The mass ratio of deionized water to acidic polysaccharide is 1:0.005 to 0.02; The amount of inorganic metal salt added is 0.01 to 0.2 wt% of the mass of deionized water.

2. The preparation method according to claim 1, characterized in that, The acidic polysaccharide is selected from one or more of the following: hyaluronic acid, xanthan gum, galvanic gum, vinca gum, pectin, sodium alginate, carrageenan, fucoidan, and ulva polysaccharide.

3. The preparation method according to claim 1, characterized in that, The inorganic metal salt is selected from one or more of the following: calcium chloride, magnesium chloride, magnesium sulfate, sodium chloride, zinc chloride, zinc sulfate, potassium chloride, ferrous chloride, ferric chloride, aluminum chloride, and copper chloride.

4. The preparation method according to claim 1, characterized in that, In step S3, the stirring rate is 1000-1400 rpm and the stirring time is 10-30 min.

5. An adhesive material with reversible, stretchable, universal adhesion, characterized in that, The adhesive material is prepared by the preparation method according to any one of claims 1-4, wherein the adhesive material is a three-dimensional dynamic network structure formed by self-assembly of acidic polysaccharide molecular chains as the backbone through non-dynamic covalent interactions.

6. The adhesive material according to claim 5, characterized in that, The viscosity range of the adhesive material is 10 to 1000 Pa·s.

7. An adhesion device, characterized in that, Includes a substrate and an adhesive material as described in any one of claims 5-6 coated on the substrate.

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