Functionalized liquid metal-based temperature response type hydrogel material and preparation method thereof

Abstract

The invention relates to a functional liquid metal-based temperature-responsive hydrogel material and a preparation method thereof, and belongs to the technical field of functional polymer hydrogel materials.The preparation method comprises the following steps that a temperature-responsive hydrogel composite material comprises a hydrophobic association polymer gel and a hydrogel monomer, the hydrophobic association polymer gel comprises a hydrophobic association polymer monomer, a functional filler and an initiator. The functional filler is liquid metal gallium with the edge modified by graphene oxide, and has triple functions: firstly, the functional filler is used as an electrostatic crosslinking node to form a crosslinking network with anionic ionic liquid; secondly, dynamic repair is promoted, and Ga < 3 + > is released to promote dynamic bond recombination. In addition, as a functional filler, the hydrogel is endowed with excellent photo-thermal and electro-thermal conversion performance, and the multi-stimulus response capability is enhanced. The composite material realizes structural assembly by means of hydrophobic association, shows reversible phase change and repeated self-assembly characteristics under various stimuli such as photo-thermal, electric heating, direct heating and the like, and has wide application potential.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of functional polymer hydrogel materials, and in particular to a functionalized liquid metal-based temperature-responsive hydrogel material and a preparation method thereof. Background Art

[0002] Thermosensitive hydrogels are a class of smart materials that reversibly swell or shrink within a specific temperature range and are widely used in areas such as controlled drug release, tissue engineering, and smart flexible actuators. However, conventional thermosensitive hydrogels face the challenge of slow temperature response. Furthermore, because their research has primarily focused on temperature-responsive properties, they struggle to meet the requirements of multifunctional integrated systems, such as electrical conductivity, photothermal conversion, or self-healing capabilities. This limitation restricts their application in complex applications. Therefore, researchers are currently attempting to impart photothermal responsiveness to thermosensitive hydrogels by adding photothermal fillers. However, conventional photothermal materials suffer from several drawbacks that significantly impact their performance and application prospects. First, carbon-based materials, such as graphene (Gr), have poor dispersion in aqueous phases and are prone to agglomeration, resulting in reduced photothermal conversion efficiency in composite materials. To overcome this issue, surface modification of Gr is often required, which not only increases the complexity of the preparation process but can also affect the material's performance. Second, the high cost and complex preparation process of noble metal nanoparticles make their large-scale industrial application a significant challenge. In addition, traditional initiators, such as persulfates, usually need to be activated at higher temperatures, which may cause some hydrogel monomers (such as N-hydroxyacrylamide (NHA)) to self-crosslink or decompose, thereby affecting the structure and properties of the hydrogel.

[0003] Gallium-based liquid metal (GLM) is a typical representative of the liquid metal family. It not only possesses excellent properties such as room-temperature fluidity, high thermal conductivity, and low toxicity, but is also an innovative material with unique functional characteristics. As a functional filler, GLM imparts excellent electrical conductivity, self-healing properties, and photothermal synergy to hydrogels, improving photothermal conversion efficiency and expanding its application areas. However, GLM still faces several challenges in practical application. First, GLM has a high surface tension, which makes it less compatible with polymers and increases its preparation difficulty. Second, GLM is easily oxidized, and the formation of an oxide layer (Ga2O3) not only reduces its fluidity but also affects its thermal conductivity. Furthermore, its inherently poor light absorption requires surface modification to improve light absorption. Furthermore, issues such as leakage and compatibility with other materials have limited its development in specialized applications. Summary of the Invention

[0004] The present invention aims to provide a functionalized liquid metal-based temperature-responsive hydrogel material and preparation method, addressing the limitations of traditional thermosensitive hydrogels, such as slow temperature response, difficulty achieving dynamic reversibility, and lack of multimodal triggering capabilities (such as photothermal / electrothermal synergy). This innovative temperature-responsive hydrogel composite avoids the use of traditional initiators. By introducing a hydrophobic associating polymer gelator and employing a simple ultrasonic process, it efficiently initiates the polymerization of hydrogel monomers. Furthermore, improvements are proposed to address the issues of gallium-based liquid metal (GLM) as a functional filler, such as high surface tension, easy oxidation, and poor photothermal conversion. Furthermore, the introduction of functionalized liquid metal as a functional filler not only overcomes these technical bottlenecks but also imparts excellent performance to the temperature-responsive hydrogel composite, promoting its application in complex environments.

[0005] The method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material according to the present invention specifically comprises the following steps: S1, ultrasonically mixing a functional filler, liquid metal, and a mixed solution of anhydrous ethanol and deionized water to obtain a functionalized liquid metal nanosuspension; S2, sequentially adding the hydrophobically associating polymer monomer, the initiator, and the functionalized liquid metal nanosuspension prepared in step S1 dropwise into dimethyl sulfoxide, stirring and blending to form a hydrophobically associating polymer gel, and washing, centrifuging, and drying to obtain a dark gray solid hydrophobically associating polymer gel; S3. Dissolve the hydrogel monomer and deionized water evenly to obtain a hydrogel monomer solution; stir and mix the hydrophobic associating polymer gelling agent and the hydrogel monomer solution prepared in step S2 evenly to obtain a temperature-responsive hydrogel composite material precursor; and after sonication, obtain a temperature-responsive hydrogel composite material.

[0006] As a further improvement of the present invention, in step S1, the functional material is at least one of carbon nanotubes (CNT), hexagonal boron nitride (h-BN), and edge oxide graphene (EOG).

[0007] As a further improvement of the present invention, in step S1, the liquid metal is a gallium-based liquid metal, at least one of metallic gallium (Ga), gallium-indium alloy (EGaIn, 85.8% Ga, 14.2% In), gallium-tin alloy (EGaSn, 91.7% Ga, 8.3% Sn), and gallium-indium-tin alloy (EGaInSn, 68.5%, 21.5% In, 10.0% Sn).

[0008] As a further improvement of the present invention, the mass ratio of the mixed solution of anhydrous ethanol and deionized water described in step S1 is (3-5):1; the specific conditions of the ultrasonication described in step S1 are as follows: in an ice water bath, the ultrasonication interval is 0.2-0.6s, the ultrasonication power is 60-90% of 12000 W, and the ultrasonication time is 15-60 min.

[0009] As a further improvement of the present invention, in step S2, the hydrophobic associating polymer monomer is a urea monomer, octadecyl methacrylate and a hydrophobic ionic liquid; the hydrophobic ionic liquid is at least one of 1-(4-allylbenzyl)-3-(3-aminopropyl)imidazolium hexafluorophosphate ([ABAIM]PF6), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), 1-butyl-3-methylimidazolium bistrifluoromethanesulfonyl imide ([BMIM][NTf2]), and 1-octyl-3-methylimidazolium hexafluorophosphate ([OMIM][PF6]); and the initiator is azobisisobutyronitrile (AIBN).

[0010] As a further improvement of the present invention, in step S2, the mass ratio of the hydrophobic associating polymer monomer to the functionalized liquid metal is 6-12:1; and the molar ratio of the urea monomer, octadecyl methacrylate and hydrophobic ionic liquid is 1:1:0-0.5.

[0011] As a further improvement of the present invention, the specific conditions for stirring and blending in step S2 are magnetic stirring for 12 to 36 hours at a speed of 300 rpm / min in an oil bath at 70-90°C; the specific conditions for washing are 2 to 5 washes, and the solvents are dimethyl sulfoxide and anhydrous ethanol; the specific conditions for centrifugation are a speed of 6000-9000 rpm and a time of 5-15 min; the specific conditions for drying in step S2 are vacuum drying at a temperature of 30-50°C and a time of 12-48 h.

[0012] As a further improvement of the present invention, the hydrogel monomer in step S3 is at least one of acrylamide (AM), N-hydroxyacrylamide (NHM), acrylic acid (AA), sodium alginate (SA), chitosan (CS), and gelatin.

[0013] As a further improvement of the present invention, the mass ratio of the hydrophobic associating polymer gelling agent to the hydrogel monomer in step S3 is 1:20-1; the stirring and mixing is specifically performed under the conditions of room temperature, a rotation speed of 300-600 rpm, and magnetic stirring for 5-10 min; the ultrasonication is specifically performed in a room temperature water bath, a power of 300 W, and a time of 30-120 min.

[0014] As a further improvement of the present invention, the functionalized liquid metal-based temperature-responsive hydrogel material, the temperature-responsive hydrogel composite material includes a hydrophobic associating polymer gelator and a hydrogel monomer; the hydrophobic associating polymer gelator includes a hydrophobic associating polymer monomer, a functional filler and an initiator; the functional filler is composed of liquid metal gallium modified with edge graphene oxide, has a "core-shell" structure, and has a particle size of 150~800 nm.

[0015] As a further improvement of the present invention, the functionalized liquid metal-based temperature-responsive hydrogel material and the temperature-responsive hydrogel composite material have the characteristic of repeated self-assembly; the repeated self-assembly performance undergoes a reversible phase change under external stimuli such as photothermal, electrothermal and direct heating, and the phase change triggers the dissociation / recombination of dynamic hydrophobic associations, manifesting as repeated self-assembly cycles of gel-sol-gel; the phase change temperature range is 42.06-65.54°C.

[0016] As a further improvement of the present invention, the functionalized liquid metal-based temperature-responsive hydrogel material, the temperature-responsive hydrogel composite material has rapid temperature responsiveness and excellent light-to-heat conversion performance; the temperature-responsive hydrogel composite material prepared by adding edge-modified graphene oxide-modified liquid metal gallium, under a light intensity of 100 mW / cm 2 Under the condition of 420 s, its surface temperature is 40.3℃.

[0017] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention uses a simple ultrasonic process to prepare functionalized liquid metal. Liquid metal gallium (Ga) is encapsulated by the functional material edge graphene oxide (EGO) to obtain functionalized liquid metal gallium (EGa) with a "core-shell" structure and a particle size of 150-800 nm. The introduction of EGO not only effectively encapsulates the metal Ga, preventing it from oxidizing to gallium trioxide (Ga2O3), but also avoids its leakage. This method is simple, environmentally friendly, and can effectively improve the stability and functionality of the material.

[0018] (2) The EGa prepared by the present invention has three functions: first, as an electrostatic cross-linking node, the surface positive charge and the anionic ionic liquid form a cross-linking network through electrostatic interaction. Second, it promotes dynamic repair and releases Ga 3+ It promotes dynamic bond reorganization. In addition, as a functional filler, it gives the hydrogel excellent photothermal and electrothermal conversion properties and enhances its multi-stimulus responsiveness.

[0019] (3) The temperature-responsive hydrogel composite material prepared by the present invention is formed by hydrophobic association of a hydrophobic associating polymer gelator and a hydrogel monomer.

[0020] (4) The temperature-responsive hydrogel composite material prepared by the present invention has the characteristic of repeated self-assembly and undergoes a reversible phase transition under external stimuli such as photothermal, electrothermal and direct heating. The phase transition triggers the dissociation and recombination of dynamic hydrophobic associations, which manifests as a gel-sol-gel self-assembly cycle. The phase transition temperature range is 42.06-65.54℃, which effectively realizes the repeated use of the material and has broad application prospects.

[0021] (5) The temperature-responsive hydrogel composite material prepared by the present invention has rapid temperature responsiveness and excellent light-to-heat conversion performance. 2 Under the condition of 420 s, its surface temperature is 40.3℃. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The present invention is a flow chart of a method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material.

[0023] Figure 2 (a) and (b) are the particle size distribution diagram and X-ray diffraction analysis (XRD) diagram of EGa0 and EGa powders prepared in Comparative Example 2 and Example 1, respectively.

[0024] Figure 3 These are the test results of the total spectrum and C 1s spectrum corresponding to the X-ray photoelectron spectroscopy (XPS) of EGa0 and EGa prepared in Example 1 and Comparative Example 2.

[0025] Figure 4 This is the density functional theory (DFT) calculation analysis diagram of EGa prepared in Example 1.

[0026] Figure 5 (a) and (b) are scanning electron microscope (SEM) and corresponding energy dispersive spectrometer (EDS) images of EGa0 and EGa powders prepared in Comparative Example 2 and Example 1, respectively.

[0027] Figure 6 The H NMR spectrum of the hydrophobically associating polymer gel prepared in Example 1 ( 1 H-NMR) test results.

[0028] Figure 7 These are the SEM and EDS test results of the hydrophobic associating polymer gel prepared in Example 1.

[0029] Figure 8 (a) and (b) are the actual pictures of the temperature-sensitive hydrogel composite materials of Comparative Example 1 and Example 1 before and after heating, respectively.

[0030] Figure 9 This is the test result of differential scanning calorimetry (DSC) of the temperature-sensitive hydrogel composite material prepared in Example 1.

[0031] Figure 10 This is a diagram demonstrating the mechanism of the temperature-sensitive hydrogel composite material prepared in Example 1 during the heating and cooling processes.

[0032] Figure 11 (a), (b) and (c) are device diagrams and infrared photos of the photothermal conversion test of the hydrogel composite materials prepared in Comparative Example 1 and Example 1, respectively.

[0033] Figure 12 (a) The hydrogel composite materials prepared in Comparative Example 1 and Example 1 under 100 mW / cm 2 Temperature-time variation curve of the surface of the hydrogel composite material under different light intensities; (b) is the temperature-time variation curve of the surface of the hydrogel composite material under different light intensities in Example 1. DETAILED DESCRIPTION

[0034] The present invention provides a method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material. In order to make the objectives, technical solutions and advantages of the present invention clearer and more specific, the present invention is further described in conjunction with specific embodiments and accompanying drawings.

[0035] Example 1 like Figure 1 As shown, the preparation method of a functionalized liquid metal-based temperature-responsive hydrogel material of the present invention is prepared by the following steps: Step 1: Add 2.0 mg of edge graphene oxide (EGO) and 0.2 g of liquid metal gallium (Ga) to a 5 ml mixture of anhydrous ethanol and deionized water (4:1). The mixture is then ultrasonicated for 30 min in an ice-water bath at 70% of 12,000 W with an interval of 0.4 s. The resulting suspension is an EGa nanosuspension. Step 2: 2 mmol of urea monomer (UM), 2 mmol of octadecyl methacrylate (SMA), 1 mmol of 1-(4-allylbenzyl)-3-(3-aminopropyl)imidazolium hexafluorophosphate ([ABAIM]PF6), 0.14 mmol of azobisisobutyronitrile (AIBN) and the EGa nanosuspension prepared above were added dropwise to 50 mL of DMSO in sequence. The mixture was reacted at 85°C for 24 h to obtain a hydrophobic associating polymer gel. After the reaction, the mixture was washed three times with dimethyl sulfoxide and anhydrous ethanol and centrifuged at 8000 rpm for 10 min. The mixture was then dried in a vacuum environment at 30°C for 24 h to obtain a dark gray solid hydrophobic associating polymer gel. Step 3: Add 2.5 g acrylamide (Am) and 0.5 g N-hydroxyacrylamide (NHA) to 5 ml deionized water, and magnetically stir at room temperature at a speed of 600 rpm for 2 h to obtain an Am / NHA mixed solution; then, add 0.3 g hydrophobic associating polymer gelator to the Am / NHA mixed solution, and ultrasonicate for 60 min in a room temperature water bath at a power of 300 W to obtain a functionalized liquid metal-based temperature-responsive hydrogel composite material.

[0036] Examples 2-3 Examples 2 and 3 provide a method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material. Compared with Example 1, the difference is that in step 3, the masses of the hydrophobic associating polymer gelator are 0.24 g and 0.36 g, respectively. The rest are the same as in Example 1 and are not repeated here.

[0037] Comparative Example 1 Comparative Example 1 provides a method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material. Compared with Example 1, the difference is that steps 1 and 2 are removed, and in step 3, the hydrophobic associating polymer gelator is replaced with an initiator potassium persulfate (KPS) with a mass of 25 mg of KPS. The rest is the same as Example 1 and will not be repeated here.

[0038] Comparative Example 2 Comparative Example 2 provides a preparation method of a liquid metal-based photothermal water gel composite material. Compared with Example 1, the difference is that EGO is not added in step 1, and the EGa nanosuspension in step 1 is replaced with EGa0 nanosuspension. The rest is the same as Example 1 and will not be repeated here.

[0039] The EGa and EGa0 nanosuspensions prepared in Example 1 and Comparative Example 2 were subjected to particle size analysis and X-ray diffraction analysis (XRD), and the results were as follows: Figure 2As shown in (a) and (b).

[0040] Figure 2 It is revealed that the introduction of EGO can effectively promote the dispersion of metallic Ga, and its particle size is reduced from 468.7 nm (Ga) to 350.9 nm (EGa). Its particle size distribution is as follows Figure 2 (a) In addition, the introduction of EGO can effectively prevent the oxidation of metal Ga to Ga2O3, as shown in the following example: Figure 2 (b) shown.

[0041] The EGa and EGa0 particles prepared in Example 1 and Comparative Example 2 were subjected to X-ray photoelectron spectroscopy (XPS), density functional theory (DFT), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), and the results were as follows: Figure 3 、 Figure 4 and Figure 5 As shown in (a) and (b).

[0042] Figure 3 It is revealed that the introduction of EGO effectively covers the metallic Ga, and the incorporation of metallic Ga enhances the bonding between EGO and Ga, and there is a potential Ga-EGO crosslink between the two; in addition, Figure 4 It further reveals that there is a strong interaction between EGO and Ga. There is a large amount of electron transfer on the interface between EGO and Ga, and these electron transfers mainly come from the interaction between O atoms and benzene rings. This indicates that there is a strong interaction between these positions and the empty orbitals of metal Ga. At the same time, it prevents the oxidation of Ga and has a good coating effect on Ga. The results are as follows Figure 5 (a) (EGa0) and (b) (EGa) are shown.

[0043] The hydrophobic associating polymer gel prepared in Example 1 was subjected to nuclear magnetic resonance spectroscopy ( 1 H-NMR), SEM and EDS tests, the results of which are as follows Figure 6 and 7 shown.

[0044] With urea monomer 1 Compared with H-NMR, the proton signal of -C=CH2- of the hydrophobic associating polymer gelator disappeared, indicating that the urea monomer was consumed during the polymerization process. At the same time, the proton signal of -NH-C=O in the hydrophobic associating polymer gelator (located in regions a and b) was weak but both appeared, proving that the urea group was successfully grafted onto the polymer chain. In addition, a new benzene ring proton signal (located in region f) was observed in the hydrophobic associating polymer gelator. The appearance of this signal indicates that 1-(4-allylbenzyl)-3-(3-aminopropyl)imidazolium hexafluorophosphate was successfully grafted onto the polymer ( Figure 6At the same time, it can be observed from its SEM and EDS that the gel contains element Ga ( Figure 7 ). In summary, the hydrophobic associating polymer gel has been successfully prepared.

[0045] The temperature-responsive composite hydrogels prepared in Example 1 and Comparative Example 1 were subjected to physical display, DSC testing and mechanism demonstration, and the results are as follows: Figure 8 (a), (b), Figure 9 and Figure 10 shown.

[0046] Figure 8 Optical photos of the hydrogel composite materials of Example 1 (containing a hydrophobic associating gelling agent) and Comparative Example 1 (containing a traditional initiator, potassium persulfate) are shown. Figure 8 (a) shows that the composite hydrogel prepared by traditional initiators lacks temperature responsiveness and cannot achieve dynamic reversible phase transition. Figure 8 In (b), EGa gives the composite hydrogel a characteristic gray-black appearance. At the same time, the addition of the hydrophobic associating gelling agent shows significant temperature sensitivity. In addition, the DSC test results show that the sol-gel transition temperature of the composite hydrogel with the addition of the hydrophobic associating gelling agent is 42.06-65.04℃ ( Figure 9 ). It was confirmed that the composite hydrogel can trigger a reversible sol-gel transition during heating / cooling cycles, and successfully constructed a thermally responsive dynamic network based on the hydrophobic association mechanism ( Figure 10 ).

[0047] The hydrogel composite materials prepared in Example 1 and Comparative Example 1 were Figure 11 The device shown in (a) was subjected to a photothermal conversion test. A xenon lamp was used as a simulated light source, and the surface temperature change of the hydrogel composite material was recorded in real time using a GThermalIR infrared thermal imaging analyzer (light intensity: 100 mW / cm 2 , 200 mW / cm 2 and 300 mW / cm 2 ).

[0048] Figure 11 and Figure 12 It is revealed that the temperature-responsive composite hydrogel material prepared in Example 1 has excellent light-to-heat conversion performance, such as Figure 11 (b), (c) and Figure 12 (a) shows that at 100 mW / cm 2 Under the light intensity of , the composite hydrogel material prepared in Comparative Example 1 without adding the hydrophobic associating gelling agent has almost no photothermal conversion ability. Figure 11(b) It can be seen that after 240 s of illumination, the surface temperature of the hydrogel composite material has almost no significant change. At the same time, further analysis shows that with the extension of the illumination time (420 s), the temperature gradually rises (35.6 ° C). This is mainly attributed to the gradual increase in the temperature of the tin foil at the bottom of the sample, which promotes the heat to be transferred from the bottom to the surface of the hydrogel, resulting in a gradual increase in its surface temperature. In contrast, the composite hydrogel material prepared in Example 1 has excellent light-heat conversion ability, as shown in FIG. Figure 11 As shown in Figures 12(c) and 12(a), under the same light intensity, the surface temperature of the hydrogel composite material increased from 24.6°C to 40.3°C, demonstrating excellent photothermal response performance. Furthermore, as the light intensity increased, the photothermal conversion capacity of the composite hydrogel material prepared in Example 1 gradually increased (Figure 12(b)), indicating that its photothermal performance can be enhanced with changes in external light conditions.

[0049] The above examples are only used to illustrate the preferred embodiments of the present invention and do not constitute a limitation on the scope of protection of the present invention. Any modification, equivalent replacement or optimization improvement made within the technical concept and principle framework of the present invention shall be deemed to fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material, comprising the following steps: S1, ultrasonically mixing the functional material, liquid metal, and a mixed solution of anhydrous ethanol and deionized water to obtain a functionalized liquid metal nanosuspension; S2, sequentially adding a hydrophobic associating polymer monomer, an initiator, and the functionalized liquid metal nanosuspension prepared in step S1 dropwise into dimethyl sulfoxide, stirring and blending to form a hydrophobic associating polymer gel, and washing, centrifuging, and drying to obtain a dark gray solid hydrophobic associating polymer gel powder; S3, dissolving the hydrogel monomer and deionized water uniformly to obtain a hydrogel monomer solution; The hydrophobically associating polymer gelling agent and the hydrogel monomer solution prepared in step S2 are stirred and mixed uniformly to obtain a temperature-responsive hydrogel composite material precursor, and after sonication, a temperature-responsive hydrogel composite material is obtained.

2. The method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material according to claim 1, characterized in that: The functional material described in step S1 is at least one of carbon nanotubes (CNTs), hexagonal boron nitride (h-BN), and edge-oxidized graphene (EOG); the liquid metal described in step S1 is gallium-based liquid metal, at least one of metallic gallium (Ga), gallium-indium alloy (EGaIn, 85.8% Ga, 14.2% In), gallium-tin alloy (EGaSn, 91.7% Ga, 8.3% Sn), and gallium-indium-tin alloy (EGaInSn, 68.5%, 21.5% In, 10.0% Sn); the mass ratio of the mixed solution of anhydrous ethanol and deionized water described in step S1 is (3-5):1; the specific conditions of the ultrasonication described in step S1 are as follows: in an ice water bath, the ultrasonication interval is 0.2-0.6 s, the ultrasonication power is 60-90% of 12000 W, and the ultrasonication time is 15-60 min.

3. The method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material according to claim 1, characterized in that: The hydrophobic associating polymer monomer in step S2 is a urea monomer, octadecyl methacrylate and a hydrophobic ionic liquid; the hydrophobic ionic liquid is at least one of 1-(4-allylbenzyl)-3-(3-aminopropyl)imidazolium hexafluorophosphate ([ABAIM]PF6), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), 1-butyl-3-methylimidazolium bistrifluoromethanesulfonimide ([BMIM][NTf2]), and 1-octyl-3-methylimidazolium hexafluorophosphate ([OMIM][PF6]); the initiator is azobisisobutyronitrile (AIBN); the mass ratio of the hydrophobic associating polymer monomer to the functionalized liquid metal is 6-12:1; and the molar ratio of the urea monomer, octadecyl methacrylate and the hydrophobic ionic liquid is 1:1:0-0.

5.

4. The method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material according to claim 1, wherein: The specific conditions for the stirring and blending in the step S2 are as follows: in an oil bath at 70-90°C, at a speed of 300 rpm / min, magnetic stirring for 12-36 hours; the specific conditions for the washing in step S2 are as follows: the number of washes is 2-5 times, and the solvent is dimethyl sulfoxide and anhydrous ethanol; the specific conditions for the centrifugation in step S2 are as follows: the speed is 6000-9000 rpm, and the time is 5-15 minutes; the specific conditions for the drying in step S2 are vacuum drying, the temperature is 30-50°C, and the time is 12-48 hours.

5. The method for preparing a functionalized liquid metal-based temperature-responsive hydrogel material according to claim 1, characterized in that: The hydrogel monomer in step S3 is at least one of acrylamide (AM), N-hydroxyacrylamide (NHM), acrylic acid (AA), sodium alginate (SA), chitosan (CS), and gelatin; the mass ratio of the hydrophobic associating polymer gelator to the hydrogel monomer in step S3 is 1:20-1; the stirring and mixing in step S3 is specifically performed at room temperature, at a speed of 300-600 rpm, and with magnetic stirring for 5-10 minutes; the ultrasonication is specifically performed in a room temperature water bath at a power of 300 W for 30-120 minutes.

6. A functionalized liquid metal-based temperature-responsive hydrogel material, characterized in that: The method is prepared by any one of claims 1 to 5.

7. The functionalized liquid metal-based temperature-responsive hydrogel material according to claim 6, characterized in that: The temperature-responsive hydrogel composite material includes a hydrophobic associating polymer gelator and a hydrogel monomer; the hydrophobic associating polymer gelator includes a hydrophobic associating polymer monomer, a functional filler and an initiator; the functional filler is composed of liquid metal gallium modified with edge graphene oxide, has a "core-shell" structure, and has a particle size of 150-800 nm.

8. The functionalized liquid metal-based temperature-responsive hydrogel material according to claim 6, characterized in that: The temperature-responsive hydrogel composite material has the characteristic of repeated self-assembly; the repeated self-assembly performance undergoes a reversible phase transition under external stimuli such as photothermal, electrothermal and direct heating, and the phase transition triggers the dissociation / reorganization of dynamic hydrophobic associations, manifesting as repeated self-assembly cycles of gel-sol-gel; the phase transition temperature range is 42.06-65.54°C.

9. The functionalized liquid metal-based temperature-responsive hydrogel material according to claim 6, characterized in that: The temperature-responsive hydrogel composite material has rapid temperature responsiveness and excellent light-to-heat conversion performance; the temperature-responsive hydrogel composite material prepared by adding edge-modified graphene oxide-modified liquid metal gallium has a high temperature responsiveness and excellent light-to-heat conversion performance under a light intensity of 100 mW / cm 2 Under the condition of 420 s, its surface temperature is 40.3℃.

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