Bionic water-triggered enhanced supramolecular polymer as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high polymer materials and biomimetic materials, and particularly relates to a biomimetic water-triggered enhanced supramolecular polymer as well as a preparation method and application thereof. The preparation method comprises the following steps: heating and mixing cellulose and ionic liquid to obtain cellulose ionic gel; performing water replacement on the cellulose ionic gel to obtain cellulose hydrogel; mixing the cellulose hydrogel and a methyl methacrylate polymer solution for polymerization reaction to obtain a cellulose / polymethyl methacrylate supramolecular system; and exposing the cellulose / polymethyl methacrylate supramolecular system to a water-based environment to obtain the bionic water-triggered enhanced supramolecular polymer. The bionic water-triggered enhanced supramolecular polymer provided by the invention shows good mechanical properties and weather resistance, and has a wider use space compared with bioplastics and traditional petrochemical plastics. Meanwhile, the hydrogel has good biocompatibility, recoverability and water resistance (that is, high performance is kept in a water environment), and the actual application is wide.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials and biomimetic materials technology, specifically relating to a biomimetic water-triggered enhanced supramolecular polymer, its preparation method, and its application. Background Technology

[0002] The development of high-performance synthetic polymers typically faces challenges such as limited reinforcement methods, demanding processing conditions (e.g., high temperature and pressure, leading to resource and energy waste), or reliance on toxic and harmful solvents. While existing technologies have reported using solvent molecule stimulation to modulate material structure, commonly used organic solvents (such as acetone and ethanol) suffer from toxicity and flammability, and offer limited performance improvements, resulting in insufficient mechanical properties, high production costs, poor weather resistance, and potential biotoxicity. Furthermore, the molding of existing polymers largely suffers from slow molding times, and current bio-based polymers exhibit poor water resistance, significantly limiting their application.

[0003] On the other hand, biological systems in nature (such as muscle tissue) provide excellent examples for materials design. Through mechanical training, muscles can promote thickening of muscle fibers and densification of cellular networks, achieving a dynamic, progressive increase in strength of up to three times. However, applying this bio-inspired, gentle, and efficient structural reinforcement strategy to synthetic polymers remains a significant challenge. Therefore, there is an urgent need to develop novel biomimetic reinforced polymers that are environmentally friendly, easy to operate, and can significantly improve the overall properties of polymers. Summary of the Invention

[0004] The purpose of this invention is to provide a biomimetic water-triggered enhanced supramolecular polymer, its preparation method, and its applications. The biomimetic water-triggered enhanced supramolecular polymer provided by this invention exhibits excellent mechanical properties and weather resistance (temperature range up to -196℃ to 180℃), offering a wider range of applications compared to bioplastics and traditional petrochemical plastics. Simultaneously, it possesses good biocompatibility, recyclability, and water resistance (i.e., maintaining high performance in aquatic environments), making it suitable for a wide range of practical applications.

[0005] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a method for preparing a biomimetic water-triggered enhanced supramolecular polymer, comprising the following steps: Cellulose and an ionic liquid are heated and mixed to obtain a cellulose ionic gel, wherein the ionic liquid is 1-butyl-3-methylimidazolium chloride. The cellulose ionogel was subjected to water replacement to obtain a cellulose hydrogel; The cellulose hydrogel and methyl methacrylate (MMA) polymerization solution are mixed and polymerized to obtain a cellulose / polymethyl methacrylate supramolecular system. The methyl methacrylate polymerization solution includes methyl methacrylate, a crosslinking agent, an initiator, and an organic solvent. The cellulose / polymethyl methacrylate supramolecular system was exposed to an aqueous environment, allowing water molecules to permeate into the network structure of the cellulose / polymethyl methacrylate supramolecular system, resulting in a biomimetic water-triggered enhanced supramolecular polymer.

[0006] Preferably, the cellulose is lignocellulose; the degree of polymerization of the cellulose is 1400~1500.

[0007] Preferably, the heating and mixing temperature is 80~90℃, the heating and mixing is carried out under stirring conditions, the stirring speed is 500~700r / min, and the time is 5~6h.

[0008] Preferably, the mass ratio of the cellulose hydrogel to the methyl methacrylate polymer solution is 1:2~4; the organic solvent is dimethyl sulfoxide; the mass ratio of the methyl methacrylate to the organic solvent is (4~6):(3~5); the mass percentage of the crosslinking agent in the methyl methacrylate polymer solution is 0.1~0.5%; and the mass percentage of the initiator is 0.8~1.2%.

[0009] Preferably, the polymerization reaction is carried out at a temperature of 75-85°C for 6-10 hours.

[0010] Preferably, the preparation method of the 1-butyl-3-methylimidazolium chloride includes the following steps: The 1-methylimidazolium liquid and 1-chlorobutane were mixed and reacted to obtain the 1-butyl-3-methylimidazolium chloride; the mass ratio of the 1-methylimidazolium liquid to 1-chlorobutane was (82~83):(92~93).

[0011] Preferably, the reaction temperature is 80~90℃, the reaction is carried out under stirring conditions, and the stirring time is 10~12h.

[0012] Preferably, the cellulose / polymethyl methacrylate supramolecular system is exposed to an aqueous environment for 10 min to 2 h.

[0013] This invention provides a biomimetic water-triggered enhanced supramolecular polymer prepared by the preparation method described in the above technical solution.

[0014] This invention provides the application of the biomimetic water-triggered enhanced supramolecular polymer described above in packaging, structural components, or biocompatible devices.

[0015] This invention provides a method for preparing a biomimetic water-triggered enhanced supramolecular polymer, comprising the following steps: heating and mixing cellulose and an ionic liquid to obtain a cellulose ionic gel, wherein the ionic liquid is 1-butyl-3-methylimidazolium chloride; replacing the cellulose ionic gel with water to obtain a cellulose hydrogel; mixing the cellulose hydrogel with a methyl methacrylate (MMA) polymerization solution to perform a polymerization reaction to obtain a cellulose / polymethyl methacrylate (PMMA) supramolecular system, wherein the MMA polymerization solution includes methyl methacrylate, a crosslinking agent, an initiator, and an organic solvent; exposing the cellulose / PMMA supramolecular system to an aqueous environment, allowing water molecules to permeate into the network structure of the cellulose / PMMA supramolecular system, thereby obtaining a biomimetic water-triggered enhanced supramolecular polymer. This invention utilizes 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) as an ionic liquid to achieve the molecularization of cellulose, constructing a cellulose spatial network structure. Subsequently, PMMA molecules are introduced through in-situ polymerization to construct a cellulose / PMMA supramolecular network. Leveraging the skeletal support of cellulose and the unique water molecule response mechanism of PMMA, a structural transformation from a stretchable network to a dense cross-linked domain is achieved under water-triggered conditions. The biomimetic water-triggered reinforced supramolecular polymer prepared by this invention exhibits a significant increase in tensile strength from 2.7 MPa to 61.7 MPa and a flexural strength reaching 97 MPa, while maintaining good structural integrity within a temperature range of -196℃ to 180℃. Furthermore, even in seawater or textile wastewater, the polymer possesses scalable hydroplasticity and reinforcing capabilities, maintaining 100% of its mechanical properties, thus allowing for customization of its geometry. Economic analysis and recycling evaluation indicate that the biomimetic water-triggered reinforced supramolecular polymer prepared by this invention has good scalability and a considerable market potential. This invention provides a biomimetic formulation for the preparation of high-performance supramolecular polymers, broadening their applications in various fields. This water-triggered strategy paves the way for designing polymers that combine high performance with environmentally friendly manufacturing processes.

[0016] Compared with the prior art, the present invention has the following significant advantages: This invention mimics the progressive strengthening mechanism of muscles under training, and uses water triggering to realize the intelligent transformation of polymers from flexible to rigid and tough. The mechanical properties (strength >60MPa, modulus ~1.8GPa) far exceed those of previously reported bioplastics. This invention uses safe and environmentally friendly water instead of toxic organic solvents as the triggering medium, and the process endows the material with unique water-dependent plasticity, allowing for customized shaping directly in water (even seawater and wastewater), while also providing processing and coloring capabilities. Its rapid moldability and ease of operation are major highlights. It reduces the use of toxic and flammable solvents and lowers reliance on energy-intensive economies. The biomimetic water-triggered enhanced supramolecular polymer prepared by this invention has excellent water resistance and biocompatibility, providing a favorable way for its application in real life.

[0017] The biomimetic water-triggered enhanced supramolecular polymer prepared by this invention exhibits excellent wide temperature range tolerance (-196℃ to 180℃) and a robust structure, far exceeding that of ordinary engineering plastics.

[0018] The biomimetic water-triggered enhanced supramolecular polymer prepared by this invention has excellent mechanical properties and strong plasticity, and has broad application prospects in fields that require lightweight, high strength, resistance to extreme environments, and customizable structures, such as special packaging, structural components, and biocompatible devices. Attached Figure Description

[0019] Figure 1 These are schematic diagrams of the structure before and after T-polymer reinforcement; Figure 2 The diagram shows the hardness and softness state and mechanical improvement of T-polymer before and after reinforcement. Figure 3 Raman curves for different water triggering times; Figure 4 XRD curves for different water trigger times; Figure 5 The effect of different water triggering times on the mechanical properties of T-polymer; Figure 5 In the figure, 'a' represents the stress-strain curves of the T-polymer at different water-triggered times; Figure 5 In the figure, b represents a comparison of the Young's modulus of T-polymers with different water triggering times; Figure 5 In the figure, 'c' represents the load-bearing capacity of the T-polymer after 2 hours of water-triggered operation. Figure 6 For molecular dynamics simulation; Figure 6 In the figure, 'a' represents the RMSD curves of cellulose and PMMA molecules before and after water triggering, as a function of time. Figure 6 In the figure, b represents the curve of the end-to-end distance between cellulose and PMMA molecules before and after water triggering as a function of time. Figure 6 In the figure, c represents the curve of the solvent-accessible area of ​​cellulose and PMMA molecules before and after water triggering as a function of time. Figure 6 In this context, d represents the comparison of the number of hydrogen bonds before and after water triggering. Figure 6 In this context, 'e' represents the comparison of electrostatic energy before and after water triggering. Figure 6 f in the figure represents the comparison of van der Waals energy before and after water triggering; Figure 7 The mechanical properties of T-polymer; Figure 7 In this context, 'a' represents the load-displacement curves from static nanoindentation tests on T-polymer and commercial plastics. Figure 7In this context, 'b' represents a comparison of the hardness of ABS, PMMA, PLA, and T-polymer. Figure 7 In the figure, 'c' represents the tensile stress-strain curves of ABS, PMMA, PLA, and T-polymer. Figure 7 In this context, d represents a comparison of the tensile strength and modulus of ABS, PMMA, PLA, and T-polymer. Figure 7 In this context, 'e' represents the tensile strength between the studied T-polymer and previously reported bioplastics. Figure 7 In this context, f represents the tensile strength and modulus of the T-polymer compared to commercial plastics. Figure 7 In the figure, g represents the flexural strength-strain curves of ABS, PMMA, PLA, and T-polymer. Figure 7 In this context, 'h' represents a comparison of the flexural strength of ABS, PMMA, PLA, and T-polymer. Figure 7 In this context, 'i' represents a comparison of the flexural moduli of ABS, PMMA, PLA, and T-polymer. Figure 8 To investigate the high-temperature resistance of T-polymer, Figure 8 In the figure, 'a' represents the comparison curve of the storage modulus of ABS, PMMA, PLA, and T-polymer, obtained through DMA testing. Figure 8 In the figure, b represents the TG curves of ABS, PMMA, PLA, and T-polymer; Figure 8 In the figure, c represents the tensile stress-strain curves of ABS, PMMA, PLA, and T-polymer after heat treatment at 180℃ for 1 hour. Figure 9 Images of T-polymer and several other plastics after being treated at high temperature for 3 hours; Figure 10 To investigate the low-temperature resistance of T-polymer; Figure 10 In the image, 'a' represents a digital image of the low-temperature resistance test conducted on T-polymer and several petrochemical plastics. Figure 10 In the figure, b represents the tensile stress-strain curve of the T-polymer after being subjected to -196℃ for 3 min. Figure 11 The water-triggered plasticization process of T-polymer; Figure 12 Optical imaging and water resistance for customizable T-polymer shapes; Figure 13 Cytotoxicity analysis of T-polymer against normal skin fibroblasts (NHDF); Figure 13 The left side of the graph shows the relative cell viability. Figure 13 The right image in the figure shows confocal live cell staining images at different extract concentrations; Figure 14 For the recyclability of T-polymer and the tensile strength and modulus of recycled T-polymer; Figure 14 The left side of the diagram shows the recyclability of T-polymer. Figure 14 The right-hand side of the figure shows the tensile strength and modulus of the recycled T-polymer; Figure 15 A comparison of the production costs of T-polymer with commercial plastics such as PP, ABS, PMMA, PA66, and PLA; Figure 16 To ensure the scalability of T-polymer in different aquatic environments; Figure 17 Comparison of the mechanical properties of T-polymer under different water environments; Figure 17 In the figure, 'a' represents the tensile stress-strain curves of T-polymer triggered by water under different water environments; Figure 17 In the figure, b represents the flexural strength-strain curve of T-polymer under different water conditions. Detailed Implementation

[0020] This invention provides a method for preparing a biomimetic water-triggered enhanced supramolecular polymer, comprising the following steps: Cellulose and an ionic liquid are heated and mixed to obtain a cellulose ionic gel, wherein the ionic liquid is 1-butyl-3-methylimidazolium chloride. The cellulose ionogel was subjected to water replacement to obtain a cellulose hydrogel; The cellulose hydrogel and methyl methacrylate (MMA) polymerization solution are mixed and polymerized to obtain a cellulose / polymethyl methacrylate supramolecular system. The methyl methacrylate polymerization solution includes methyl methacrylate, a crosslinking agent, an initiator, and an organic solvent. The cellulose / polymethyl methacrylate supramolecular system was exposed to an aqueous environment, allowing water molecules to permeate into the network structure of the cellulose / polymethyl methacrylate supramolecular system, resulting in a biomimetic water-triggered enhanced supramolecular polymer.

[0021] In this invention, unless otherwise specified, all raw materials / components used in the preparation are commercially available products well known to those skilled in the art.

[0022] This invention involves heating and mixing cellulose and an ionic liquid to obtain a cellulose ionic gel, wherein the ionic liquid is 1-butyl-3-methylimidazolium chloride.

[0023] This invention uses 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) ionic liquid as a non-derivative solvent. In this invention, the preparation method of the 1-butyl-3-methylimidazolium chloride preferably includes the following steps: mixing 1-methylimidazolium liquid and 1-chlorobutane and reacting them to obtain the 1-butyl-3-methylimidazolium chloride. The preferred mass ratio of the 1-methylimidazolium liquid to 1-chlorobutane is (82~83):(92~93), and in the examples, it can be 82.1:92.57. Before mixing, this invention preferably pre-dries the 1-methylimidazolium liquid. The preferred temperature for the pre-drying treatment is 80~90℃, and the preferred time is 1~3 hours, and in the examples, it can be 2 hours. The pre-drying treatment is preferably carried out in an oven. This invention uses the pre-drying treatment to maintain the purity of 1-methylimidazolium. In this invention, the mixing preferably includes: pre-stirring the 1-methylimidazolium, and then adding 1-chlorobutane dropwise to the 1-methylimidazolium. The preferred stirring speed is 800-1200 r / min, and in this example, it can be 1000 r / min. The dropping can be done dropwise, and the preferred dropping time is 30-40 min, and in this example, it can be 30 min. The dropping is carried out under stirring conditions, and the preferred stirring speed is 800-1200 r / min, and in this example, it can be 1000 r / min. The preferred dropping temperature is 60-70℃, and in this example, it can be 65℃; the reaction is carried out under oil bath conditions. After the dropping is complete, the preferred reaction temperature is 80-85℃, preferably 85℃. The reaction is preferably carried out under stirring conditions, and the preferred stirring speed is 800-1200 r / min, and in this example, it can be 1000 r / min. The preferred stirring time is 10-12 h, and in this example, it can be 11 h. After the reaction is complete, the reaction solution is obtained directly. In this invention, the reaction solution is preferably mixed with acetone, cooled to room temperature, and then subjected to low-temperature crystallization to obtain the 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) ionic liquid. This invention uses acetone to extract and purify the reaction solution, removing unreacted 1-methylimidazolium and 1-chlorobutane from the reaction solution. The preferred low-temperature crystallization temperature is 1~10℃, more preferably 1~8℃. The preferred low-temperature crystallization time is 10~15 h, and in the examples, it can be 12 h. This invention ensures a higher purity 1-butyl-3-methylimidazolium chloride and a high ionic liquid yield by optimizing the low-temperature crystallization temperature and time.

[0024] In this invention, the cellulose is preferably lignocellulose, and the degree of polymerization of the cellulose is preferably 1400-1500. The cellulose can be a commercially available product purchased from Aladdin.

[0025] In this invention, prior to the heating and mixing, the ionic liquid is preferably melted by heating, then mixed with cellulose, and then pre-reacted. The pre-reaction is carried out in a forced-air drying oven, and the preferred temperature is 80-85°C. The preferred pre-reaction time is 1-2 hours. The pre-reaction is carried out under stirring conditions, which can be mechanical stirring.

[0026] In this invention, the heating and mixing are carried out under oil bath conditions. The preferred heating and mixing temperature is 80-90°C, and in this embodiment, it can be 85°C. The heating and mixing are carried out under stirring conditions, and the preferred stirring speed is 500-700 r / min, and in this embodiment, it can be 600 r / min. The preferred stirring time is 5-6 hours.

[0027] In this invention, the cellulose mass percentage in the cellulose ion gel is preferably 3-5%, and in the examples it can be 4%.

[0028] After obtaining the cellulose ionogel, the present invention performs water replacement on the cellulose ionogel to obtain a cellulose hydrogel. In the present invention, the water replacement is preferably performed multiple times, and in the embodiment, it can be performed three times. The present invention preferably immerses the cellulose ionogel in water for water replacement. The water replacement is preferably performed using deionized water. Each water replacement requires replacing the deionized water. The water replacement temperature can be room temperature. The first water replacement time is preferably 10-20 minutes, then the second water replacement is performed using deionized water for 1-1.5 hours, and then the third water replacement is performed using deionized water for 1-1.5 hours.

[0029] After obtaining the cellulose hydrogel, the present invention mixes the cellulose hydrogel with a methyl methacrylate (MMA) polymerization solution for polymerization to obtain a cellulose / polymethyl methacrylate supramolecular system. In the present invention, the methyl methacrylate polymerization solution comprises methyl methacrylate, a crosslinking agent, an initiator, and an organic solvent. The organic solvent is preferably dimethyl sulfoxide (DMSO). The mass ratio of methyl methacrylate to the organic solvent is preferably (4~6):(3~5), more preferably 5:4. The crosslinking agent is preferably N,N'-methylenebisacrylamide. The initiator is preferably ammonium persulfate. The mass percentage of the crosslinking agent in the methyl methacrylate polymerization solution is preferably 0.1~0.5%, and in the examples it can be 0.5%. The mass percentage of the initiator in the methyl methacrylate polymerization solution is preferably 0.8~1.2%, and in the examples it can be 1%.

[0030] In this invention, the mass ratio of the cellulose hydrogel to the methyl methacrylate polymerization solution is preferably 1:2 to 4, more preferably 1:3. In this invention, before the polymerization reaction, the resulting mixture is preferably soaked at a low temperature of 1 to 2°C; the soaking time is preferably 5 to 7 hours, and in the examples, it can be 6 hours. In this invention, the polymerization reaction is carried out in an oven. The polymerization reaction temperature is preferably 75 to 85°C, and in the examples, it can be 80°C. The polymerization reaction time is preferably 6 to 10 hours, and in the examples, it can be 8 hours.

[0031] After obtaining the cellulose / polymethyl methacrylate supramolecular system, the present invention exposes the cellulose / polymethyl methacrylate supramolecular system to an aqueous environment, allowing water molecules to permeate into the network structure of the cellulose / polymethyl methacrylate supramolecular system, thereby obtaining a biomimetic water-triggered enhanced supramolecular polymer.

[0032] In this invention, the specific operation of exposing the cellulose / polymethyl methacrylate supramolecular system to an aqueous environment can be as follows: immersing the cellulose / polymethyl methacrylate supramolecular system in water, which can be deionized water, at room temperature. The preferred exposure time for the cellulose / polymethyl methacrylate supramolecular system to the aqueous environment is 10 min to 2 h; in the examples, it can be 10 min, 30 min, 1 h, or 2 h.

[0033] In this invention, when exposed to an aqueous environment, PMMA molecules undergo hydrophobic-driven conformational curling, inducing rearrangement and densification of the entire supramolecular network, forming reinforced cross-linking domains and enhanced hydrogen bond networks, thereby obtaining a final material with enhanced mechanical properties.

[0034] This invention provides a biomimetic water-triggered enhanced supramolecular polymer prepared by the preparation method described in the above technical solution.

[0035] This invention provides the application of the biomimetic water-triggered enhanced supramolecular polymer described above in packaging, structural components, or biocompatible devices.

[0036] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0037] Example 1 This embodiment provides a method for preparing a biomimetic water-triggered enhanced supramolecular polymer, specifically including the following steps: Step 1: Preparation of 1-Butyl-3-methylimidazolium chloride ionic liquid The ionic liquid used in this embodiment is 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), and [Bmim]Cl is used as the non-derivative solvent. First, 82.1 g of 1-methylimidazolium liquid was poured into a 250 mL three-necked flask and then placed in an oven at 85 °C for 2 h to dry it, maintaining the purity of the 1-methylimidazolium. Second, the three-necked flask containing 1-methylimidazolium was placed in a 65 °C oil bath. An electric stirrer was connected to the center hole of the flask, and glass stoppers and condensers containing anhydrous calcium chloride were placed at the two ends of the flask to maintain a dry environment inside the flask. After vigorous stirring at 1000 r / min for 30 min, 92.57 g of 1-chlorobutane was weighed and added dropwise to the three-necked flask, mixing thoroughly with the 1-methylimidazolium. The stirring speed was maintained at 1000 r / min, and the mixing time was 35 min. Third, after the addition is complete, set the oil bath temperature to 85 ℃ and stir continuously (1000 r / min) for 11 h to ensure complete reaction. Fourth, pour the liquid from the reaction into a beaker containing acetone (350 mL) and use acetone to extract and purify the product. The role of acetone is to dissolve and remove the incompletely reacted 1-methylimidazolium and 1-chlorobutane. After cooling to room temperature, place it in a refrigerator and continue to refrigerate at low temperature (1~8℃) for 12 h. At low temperature, 1-butyl-3-methylimidazolium chloride will crystallize out. After complete crystallization (12 h is chosen to ensure complete crystallization), pour out the acetone and separate to obtain the purified 1-butyl-3-methylimidazolium chloride ionic liquid.

[0038] Step 2: Preparation of cellulose hydrogel 2.084 g of commercially available lignocellulose (degree of polymerization 1400-1500) and 50 g of pre-melted ionic liquid were poured together into a three-necked flask and pre-reacted in a forced-air drying oven at 85 °C for 1 h to enhance the dissolution rate of lignocellulose under mechanical stirring. Then, the mixture was mechanically stirred at 600 r / min for 6 h in a constant-temperature oil bath at 85 °C to obtain a cellulose ion gel. The cellulose ion gel was then immersed in deionized water for three water displacements to obtain a cellulose hydrogel. The first water displacement lasted 20 min, followed by a second water displacement lasting 1 h, and a third water displacement lasting 1 h. The lignocellulose content in the cellulose ion gel was 4% by mass.

[0039] Step 3: Construction of biomimetic water-triggered enhanced supramolecular polymers 10g of cellulose hydrogel obtained in step two was placed in 30g of MMA polymerization solution, wherein the mass ratio of MMA to DMSO in the MMA polymerization solution was 5:4, and it contained 0.5% crosslinking agent (N,N'-methylenebisacrylamide) and 1% initiator (ammonium persulfate). The solution was then placed in a refrigerator at 1-2 °C for approximately 6 hours for low-temperature immersion. Subsequently, a petri dish containing the polymerization solution and the cellulose hydrogel membrane was placed in an oven at 80 °C for polymerization for 8 hours. The cellulose membrane was then peeled off from the polymerized system to obtain a cellulose / polymethyl methacrylate supramolecular system. This system was then exposed to an aqueous environment (i.e., immersed in water at room temperature without stirring for water reinforcement), allowing water molecules to penetrate into the network. During this process, PMMA molecules undergo hydrophobic-driven conformational coiling, inducing rearrangement and densification of the entire supramolecular network, forming reinforced crosslinking domains and enhanced hydrogen bond networks, thereby obtaining a final material with enhanced mechanical properties—that is, a biomimetic water-triggered reinforced supramolecular polymer. In this embodiment, the water triggering times are 10 min, 30 min, 1 h, and 2 h, respectively.

[0040] Example 2 The waste material from the biomimetic water-triggered enhanced supramolecular polymer prepared in Example 1 was recycled and pulverized into granules. These granules replaced the lignocellulose in Example 1 as the reaction raw material, and the preparation was carried out according to steps two and three of Example 1. This yielded a biomimetic water-triggered enhanced supramolecular polymer with comparable performance. This demonstrates that the biomimetic water-triggered enhanced supramolecular polymer provided by this invention can be effectively recycled and reused.

[0041] Performance testing: The tensile mechanical properties and flexural stress-strain tests of the water-triggered polymer prepared in Example 1 and various plastics were measured using a UTM2503 electromechanical universal testing machine (Shenzhen SUNS Technology Co., Ltd.). The specimens were stretched at 10 mm / min at room temperature. Flexural stress-strain tests were performed using a three-point bending mode (40 mm span between the two support points). The specimens were tested at a constant speed of 5 mm / min at room temperature. Each sample underwent five independent tests.

[0042] The biomimetic water-triggered enhanced supramolecular polymer prepared in Example 1 of this invention comprises a composite network composed of cellulose and polymethyl methacrylate (PMMA) molecules; after water-triggered treatment, the stretchable network transforms into a dense cross-linked structure, while simultaneously forming a stronger hydrogen bond network, such as... Figure 1 As shown, Figure 1The diagram shows the structure of the T-polymer prepared in Example 1 before and after reinforcement; this endows the material with unique properties, and at the same time, the material achieves a transformation from a soft state to a hard state, thereby improving its mechanical properties, such as... Figure 2 As shown, Figure 2 The graphs show the hardness and softness states and mechanical improvements of the T-polymer prepared in Example 1 before and after reinforcement. Raman spectroscopy (e.g.) Figure 3 As shown, Figure 3 Raman curves for different water trigger times), XRD (e.g.) Figure 4 As shown, Figure 4 The XRD patterns for different water-triggered times collectively demonstrate that the material becomes denser after water triggering, and that different mechanical properties can be customized as the water triggering time increases (e.g., ...). Figure 5 As shown, Figure 5 The effect of different water triggering times on the mechanical properties of T-polymer; Figure 5 In the figure, 'a' represents the stress-strain curves of the T-polymer at different water-triggered times; Figure 5 In the figure, b represents a comparison of the Young's modulus of T-polymers with different water triggering times; Figure 5 In this context, 'c' represents the load-bearing capacity of the T-polymer after 2 hours of water triggering. Molecular dynamics simulations reveal enhanced molecular interactions and configurational curling within the material (e.g., ...). Figure 6 As shown, Figure 6 For molecular dynamics simulation; Figure 6 In the figure, 'a' represents the RMSD curves of cellulose and PMMA molecules before and after water triggering, as a function of time. Figure 6 In the figure, b represents the curve of the end-to-end distance between cellulose and PMMA molecules before and after water triggering as a function of time. Figure 6 In the figure, c represents the curve of the solvent-accessible area of ​​cellulose and PMMA molecules before and after water triggering as a function of time. Figure 6 In this context, d represents the comparison of the number of hydrogen bonds before and after water triggering. Figure 6 In this context, 'e' represents the comparison of electrostatic energy before and after water triggering. Figure 6 (where f represents the van der Waals energy comparison before and after water triggering). The trigger-enhanced material exhibits excellent mechanical properties and good weather resistance. Furthermore, the material prepared using this water-triggered strategy possesses advantages such as excellent biocompatibility, recyclability, economical production costs, room-temperature plasticity, and universality to various aquatic environments.

[0043] By comparing with commercial plastics, the advantages of water triggering in improving mechanical properties are highlighted. The water-triggered polymer (T-polymer) prepared in this invention has better mechanical properties (including hardness, tensile strength, elastic modulus, flexural strength, flexural modulus, impact resistance, etc.). Figure 7 The mechanical properties of T-polymer; Figure 7 In this context, 'a' represents the load-displacement curves from static nanoindentation tests on T-polymer and commercial plastics. Figure 7 In this context, 'b' represents a comparison of the hardness of ABS plastic, polymethyl methacrylate (PMMA), polylactic acid (PLA), and T-polymer. Figure 7 In the figure, 'c' represents the tensile stress-strain curves of ABS, PMMA, PLA, and T-polymer. Figure 7 In this context, d represents a comparison of the tensile strength and modulus of ABS, PMMA, PLA, and T-polymer. Figure 7 In this context, 'e' represents the tensile strength between the studied T-polymer and previously reported bioplastics. Figure 7In the following section, AC-TPA was prepared according to the method disclosed in "Zhou G, Zhang H, Su Z, et al. A biodegradable, waterproof, and thermally processable cellulosic bioplastic enabled by dynamic covalent modification[J]. Advanced Materials, 2023, 35(25): 2301398."; BH-plastic was prepared according to the method disclosed in "Qiu Y, Zhang D, Long M, et al. Coassembly of hybrid microscale biomatter for robust, water-processable, and sustainable bioplastics[J]. Science Advances, 2025, 11(14): eadr1596."; and XPCF-3SH was prepared according to "Xia Q, Wang H, Dai Y, et al. Photosynthesis‐Inspired Enhancement of Cellulose Bioplastics Using Hemicellulose‐Derived Biodegradable Polyesters[J]. Advanced Functional Materials, 2025: CH-plastic was prepared according to the method disclosed in "Koh JJ. et al. Reprogrammable, sustainable, and 3D‐printable cellulose hydroplastic. Adv.Sci. 11, 2402390 (2024)."; BM-plastic was prepared according to the method disclosed in "Liu C, Luan P, LiQ, et al. Biodegradable, hygienic, and compostable tableware from hybrid sugarcane and bamboo fibers as plastic alternative[J]. Matter, 2020, 3(6):2066-2079."; and ESO4-PLA was prepared according to "Fang X. et al."SBPSCGM15 was prepared according to the method disclosed in "Dynamically cross-linking soybean oil and low-molecular-weight polylactic acid toward mechanically robust, degradable, and recyclable supramolecular plastics. Adv. Funct. Mater. 32, 2208623 (2022)". ABTP was prepared according to the method disclosed in "Xie D. et al. Nacre-inspired starch-based bioplastic with excellent mechanical strength and electromagnetic interference shielding. Carbohydr. Polym. 331, 121888 (2024)". CAF-7%-100 was prepared according to the method disclosed in "Guo D. et al. Conversion of bamboo into strong, waterproof, and biodegradable thermosetting plastic through cell wall structure directed manipulation. ACS Nano 18, 24414-24425 (2024)". AOST-ESO was prepared according to the method disclosed in "dynamic covalent networks. Adv. Sci. 12, e08075 (2025)". AOST-ESO was prepared according to the method disclosed in "Yang J. et al. Preparation and characterization of bioplastics from silylated cassava starch and epoxidized soybean oils. Carbohydr. Polym. 300, 120253 (2023)". Figure 7In this context, f represents the tensile strength and modulus of T-polymer compared to commercial plastics (polyethylene terephthalate (PET), polycaprolactone (PCL), polybutylene succinate (PBS), PLA, polyvinyl alcohol (PVA), polyvinyl chloride (PVC), polyhydroxyalkanoates (PHA), polybutylene terephthalate (PBAT), PMMA, and ABS plastics). Figure 7 In the figure, g represents the flexural strength-strain curves of ABS, PMMA, PLA, and T-polymer. Figure 7 In this context, 'h' represents a comparison of the flexural strength of ABS, PMMA, PLA, and T-polymer. Figure 7 In this context, 'i' represents a comparison of the flexural modulus of ABS, PMMA, PLA, and T-polymer. For example... Figure 7 As shown in Figure a, under the same nanoindentation load, T-polymer exhibits the smallest nanoindentation depth compared to plastics such as ABS, PMMA, and PLA. This is due to the dense supramolecular structure of T-polymer, resulting in an indentation hardness of 0.598 GPa. Figure 7 (b) In terms of macroscopic mechanical properties, T-polymer also exhibits attractive mechanical properties ( Figure 7 (c) has a tensile strength and Young's modulus of 61.7 MPa and 1.8 GPa, respectively. Figure 7 In terms of d), it is superior to plastics such as ABS, PMMA, and PLA. Compared with reported bio-based plastics ( Figure 7 (e) and more widely used petrochemical plastics ( Figure 7 Compared to f), T-polymer still has advantages in tensile strength and Young's modulus. It is worth noting that T-polymer also exhibits excellent flexural properties. Figure 7 The flexural strength of the material is 97 MPa, and its flexural modulus is 4.085 GPa. Figure 7 h in Figure 7 (i) Compared to various commercial plastics, it exhibits superior resistance to deformation. These excellent mechanical properties ensure the practical application of our invention.

[0044] In addition to its excellent mechanical properties, T-polymer also exhibits impressive resistance to extreme environmental conditions, providing a broad operating range and solid foundation for practical applications. We utilize dynamic mechanical analysis (DMA) to investigate the thermodynamic behavior of T-polymer. Figure 8 To investigate the high-temperature resistance of T-polymer, Figure 8 In the figure, 'a' represents the comparison curve of the storage modulus of ABS, PMMA, PLA, and T-polymer, obtained through DMA testing. Figure 8In the figure, b represents the TG curves of ABS, PMMA, PLA, and T-polymer; Figure 8 In the figure, 'c' represents the tensile stress-strain curves of ABS, PMMA, PLA, and T-polymer after heat treatment at 180℃ for 1 hour. For example... Figure 8 As shown in Figure a, the storage modulus (G') of commercial plastics (such as ABS) is almost zero at temperatures below 115°C. In contrast, the t-polymer (T-polymer) prepared in the embodiments of the present invention maintains a high G', exhibits a detectable elastic response even at 180°C, and shows no melting deformation (e.g., Figure 9 As shown, Figure 9 (Images of T-polymer and several other plastics after being treated at high temperature for 3 hours). Meanwhile... Figure 8 b in the figure confirmed that it has a high decomposition temperature, up to 290℃, and that the T-polymer still maintains a tensile strength of close to 40MPa after being treated at 180℃ for 1 hour. Figure 8 (c) In addition to high temperature resistance, T-polymer also exhibits significant low temperature stability. Figure 10 To investigate the low-temperature resistance of T-polymer; Figure 10 In the image, 'a' represents a digital image of a low-temperature resistance test conducted on T-polymer and petrochemical plastics (ABS, PLA, PMMA). Figure 10 In the figure, b represents the tensile stress-strain curve of the T-polymer after being subjected to -196℃ for 3 minutes. (Example:) Figure 10 As shown in a, even after immersion in liquid nitrogen (-196°C) for 3 minutes, the T-polymer retains its toughness and foldability, with a tensile strength exceeding 40 MPa. Figure 10 (b) In this context, all ABS, PMMA, and PLA samples exhibited significant flexural failure. This could potentially facilitate the application of T-polymer as a lightweight, cold-resistant material in aerospace and Arctic exploration equipment.

[0045] The plasticity at room temperature reduces dependence on energy and simplifies the preparation process. T-polymer's water-triggered enhancement process gives it unique shape customization, which can be completed within 15 seconds. This simple and rapid shaping method is not available in traditional methods. Figure 11 , Figure 11 The water-triggered plasticization process of T-polymer is a key feature, and compared to the poor water resistance of most bioplastics, T-polymer exhibits better water resistance. Figure 12 , Figure 12 Optical images and water resistance of T-polymer for customizable shapes. In cytotoxicity tests, T-polymer did not show any cytotoxic effects. Figure 13 , Figure 13 Cytotoxicity analysis of T-polymer against normal skin fibroblasts (NHDF); Figure 13 The left side of the graph shows the relative cell viability. Figure 13 The right-hand image shows confocal live cell staining images at different extract concentrations, demonstrating excellent biocompatibility and providing a biological basis for its practical applications. Simultaneously, T-polymer exhibits excellent recyclability, and the recycled material still possesses considerable mechanical properties, reaching up to 49 MPa. Figure 14 , Figure 14 For the recyclability of T-polymer and the tensile strength and modulus of recycled T-polymer; Figure 14 The left side of the figure shows the recyclability of the T-polymer (recycled according to the method provided in Example 2). Figure 14 The right-hand figure shows the tensile strength and modulus of recycled T-polymer. Finally, although T-polymer has a slightly higher production cost, its combination of high mechanical strength, excellent resistance to extreme environments, biocompatibility, and energy-efficient processability positions it favorably for advanced applications in the high-performance plastics market. Figure 15 , Figure 15 (Comparison of production costs between T-polymer and commercial plastics such as PP, ABS, PMMA, PA66, and PLA).

[0046] The water-triggered enhanced T-polymer method proposed in this invention is applicable to various water quality environments. Example 1 uses tap water; previously, high-salinity seawater (…) Figure 17 Seawater, sludge water containing suspended solids, and textile wastewater containing dyes (such as indigo, at a concentration of 10-20%) can all effectively mechanically strengthen water-triggered polymers, giving them molding properties. Figure 16 , Figure 16 The scalability of T-polymer in different aquatic environments and its attractive mechanical properties (for T-polymer) Figure 17 , Figure 17 Comparison of the mechanical properties of T-polymer under different water environments; Figure 17 In the figure, 'a' represents the tensile stress-strain curves of T-polymer triggered by water under different water environments; Figure 17 In the figure, b represents the flexural strength-strain curve of T-polymer under different water conditions. Furthermore, utilizing textile wastewater facilitates arbitrary and on-demand design of T-polymer coloring.

[0047] As demonstrated by the above embodiments, this invention utilizes [Bmim]Cl ionic liquid to dissolve cellulose, constructing a homogeneous cellulose molecular system, and then introduces PMMA molecules to build a cellulose / PMMA supramolecular network. This invention uses water, a green solvent, with cellulose as the framework and PMMA as the water-responsive molecule. Under water triggering, the cellulose / PMMA supramolecular network achieves structural densification and cross-linking domain formation, enhancing its hydrogen bond network and thus endowing it with unique comprehensive properties. The cross-linking domain plays a major role in this process. This invention adopts biomimetic thinking to achieve customizable material properties. The T-polymer prepared by this invention can be molded within 15 seconds, a rapid and simple molding method not available in traditional methods, demonstrating a certain degree of advancement. This invention has broad applicability in water environment selection, achieving water-triggered enhancement in various water environments (including seawater, polluted water, industrial wastewater, etc.), expanding its application scope. The T-polymer prepared by this invention exhibits good mechanical properties and weather resistance (temperature range up to -196℃ to 180℃), which offers a wider range of applications compared to some bioplastics and traditional petrochemical plastics. Furthermore, its excellent biocompatibility and recyclability play a positive role in its practical applications. Its versatility in various molding processes (including injection molding and extrusion) may make it attractive to manufacturers. Finally, its water resistance (i.e., maintaining high performance in aquatic environments) is something many bio-based materials lack.

[0048] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a biomimetic water-triggered enhanced supramolecular polymer, characterized in that, Includes the following steps: Cellulose and an ionic liquid are heated and mixed to obtain a cellulose ionic gel, wherein the ionic liquid is 1-butyl-3-methylimidazolium chloride. The cellulose ionogel was subjected to water replacement to obtain a cellulose hydrogel; The cellulose hydrogel and methyl methacrylate polymerization solution are mixed and polymerized to obtain a cellulose / polymethyl methacrylate supramolecular system. The methyl methacrylate polymerization solution includes methyl methacrylate, a crosslinking agent, an initiator, and an organic solvent. The cellulose / polymethyl methacrylate supramolecular system was exposed to an aqueous environment, allowing water molecules to permeate into the network structure of the cellulose / polymethyl methacrylate supramolecular system, resulting in a biomimetic water-triggered enhanced supramolecular polymer.

2. The preparation method according to claim 1, characterized in that, The cellulose is lignocellulose; the degree of polymerization of the cellulose is 1400~1500.

3. The preparation method according to claim 1, characterized in that, The heating and mixing temperature is 80~90℃, and the heating and mixing is carried out under stirring conditions. The stirring speed is 500~700r / min, and the time is 5~6h.

4. The preparation method according to claim 1, characterized in that, The mass ratio of the cellulose hydrogel to the methyl methacrylate polymer solution is 1:2~4; the organic solvent is dimethyl sulfoxide; the mass ratio of the methyl methacrylate to the organic solvent is (4~6):(3~5); the mass percentage of the crosslinking agent in the methyl methacrylate polymer solution is 0.1~0.5%; and the mass percentage of the initiator is 0.8~1.2%.

5. The preparation method according to claim 1 or 4, characterized in that, The polymerization reaction is carried out at a temperature of 75-85°C for 6-10 hours.

6. The preparation method according to claim 1, characterized in that, The preparation method of the 1-butyl-3-methylimidazolium chloride includes the following steps: The 1-methylimidazolium liquid and 1-chlorobutane were mixed and reacted to obtain the 1-butyl-3-methylimidazolium chloride; the mass ratio of the 1-methylimidazolium liquid to 1-chlorobutane was (82~83):(92~93).

7. The preparation method according to claim 6, characterized in that, The reaction is carried out at a temperature of 80-90°C, under stirring conditions, and the stirring time is 10-12 hours.

8. The preparation method according to claim 1, characterized in that, The cellulose / polymethyl methacrylate supramolecular system was exposed to an aqueous environment for 10 min to 2 h.

9. The biomimetic water-triggered enhanced supramolecular polymer prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the biomimetic water-triggered enhanced supramolecular polymer of claim 9 in packaging, structural components or biocompatible devices.

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