A method for fabricating and applying a photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts.

Abstract

This invention discloses a method for preparing and applying a photothermal-responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts. The method involves a UV-photothermal-responsive color-deformation bilayer hydrogel. The invention utilizes N-isopropylacrylamide and acylated modified β-cyclodextrin as raw materials, incorporating an ultrasonically treated multi-walled carbon nanotube dispersion. A photothermal-responsive hydrogel matrix I is obtained through free radical polymerization and host-guest crosslinking. Then, utilizing the reversible color change characteristics of polyacid salts under UV irradiation, N-isopropylacrylamide, acylated modified β-cyclodextrin, and ammonium molybdate tetrahydrate are dissolved in deionized water to obtain a mixed reaction solution. This reaction solution is cast onto the photothermal-responsive hydrogel matrix I. A photothermal-responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts is obtained through free radical polymerization, electrostatic interaction, and host-guest crosslinking. This robot is used as a photothermal information acquisition and encryption device material that exhibits UV-responsive color change and photothermal-responsive deformation.

Description

Technical Field

[0001] This invention relates to a method for preparing and applying a bilayer hydrogel that exhibits UV-photothermal responsive color deformation. Background Technology

[0002] Traditional hydrogels are static materials, and their limited applications are restricted by their singular properties and insensitivity to environmental changes. Therefore, stimulus-responsive hydrogels have emerged as a type of "smart" material. Currently, research on the multi-stimulus-responsive properties of hydrogels is becoming increasingly sophisticated, and smart-responsive hydrogel sensors have been applied in mechanical sensing, speech recognition, health diagnosis, energy harvesting, and signal monitoring. Compared to traditional pressure-driven and battery-driven robots, hydrogel robots use light and temperature as signal sources, enabling instantaneous on / off switching of signals, and offering advantages such as signal stability, operational flexibility, and spatial and directional specificity. By microscopically loading photothermal active components and covalently binding them to the gel network, reversible reconstruction of the photoresponsive gel network can be achieved. Macroscopically controlling the regular arrangement of photothermal active components within the gel network to construct gradients allows for anisotropic response behavior under localized light irradiation, injecting new momentum into the innovative research and development of compiler materials. Currently developed flexible hydrogel robot materials cannot simultaneously achieve high strength, excellent flexibility, and multi-stimulus-responsive functionality, making it difficult to achieve stable information acquisition, loading, encryption, and output under complex conditions. Therefore, there is an urgent need to explore new hydrogel synthesis strategies to prepare novel flexible hydrogel compilation robot materials that possess characteristics such as high mechanical strength, sensitive signal response, and strong flexibility. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention provides a method for preparing and applying a photothermal responsive bilayer hydrogel information compilation robot incorporating polyacid salts.

[0004] This invention utilizes N-isopropylacrylamide and acylated β-cyclodextrin as raw materials, incorporating an ultrasonically treated multi-walled carbon nanotube dispersion. Through free radical polymerization and host-guest crosslinking reactions, a photothermal responsive hydrogel matrix I is obtained. Then, taking advantage of the reversible color change characteristics of polyacid salts under ultraviolet light irradiation, N-isopropylacrylamide, acylated β-cyclodextrin, and ammonium molybdate tetrahydrate are dissolved in deionized water to obtain a mixed reaction solution. This reaction solution is cast onto the photothermal responsive hydrogel matrix I. Using free radical polymerization, electrostatic interactions, and host-guest crosslinking, a polyacid salt-incorporated photothermal responsive flexible bilayer hydrogel information compilation robot is obtained.

[0005] A method for fabricating a photothermally responsive flexible bilayer hydrogel incorporating polyacid salts is specifically carried out according to the following steps:

[0006] I. Preparation of acylated modified β-cyclodextrin:

[0007] ① Add β-cyclodextrin and potassium hydroxide to deionized water and stir magnetically for a period of time in a water bath at 0℃~4℃ to obtain mixed solution I;

[0008] ② Add acryloyl chloride dropwise to mixed solution I while maintaining magnetic stirring during the addition process to obtain mixed solution II;

[0009] ③ Heat the mixed solution II in a water bath and stir magnetically for a period of time, then concentrate it under vacuum using a rotary evaporator to obtain a concentrated solution;

[0010] ④ The concentrate was added dropwise into acetone to precipitate the precipitate. After being filtered under reduced pressure, the precipitate was washed with acetone, pre-frozen for a period of time, and then freeze-dried under vacuum for a period of time to obtain acylated modified β-cyclodextrin.

[0011] II. Preparation of photothermal responsive hydrogel matrix I:

[0012] ① Weigh out multi-walled carbon nanotubes and hexadecyltrimethylammonium bromide, dissolve them in deionized water, and sonicate for a period of time to obtain a multi-walled carbon nanotube dispersion;

[0013] ② Dissolve N-isopropylacrylamide, acylated modified β-cyclodextrin and N',N'-methylenebisacrylamide in deionized water, stir for a period of time, then add multi-walled carbon nanotube dispersion, continue stirring for a period of time, and then pre-cool in a -4℃ environment to obtain pre-cooled mixed solution Ⅲ.

[0014] ③ Dissolve potassium persulfate in deionized water to obtain potassium persulfate aqueous solution; add potassium persulfate aqueous solution and N,N,N',N'-tetramethylethylenediamine to pre-cooled mixed solution Ⅲ to obtain precursor solution Ⅰ;

[0015] ④ Add the precursor liquid I into the silicone mold and place it in a vacuum environment for a period of time to react, so as to obtain a mold carrying the photothermal responsive hydrogel matrix I;

[0016] III. Preparation of a bilayer hydrogel information compilation robot:

[0017] ① Dissolve N-isopropylacrylamide, acylated modified β-cyclodextrin and N',N'-methylenebisacrylamide in deionized water, stir for a period of time, add methacryloyloxyethyltrimethylammonium chloride dropwise, then add ammonium molybdate tetrahydrate, continue stirring until a homogeneous and transparent mixed solution is obtained, place it in a -4℃ environment for pre-cooling, and obtain the pre-cooled mixed solution IV.

[0018] ② Dissolve potassium persulfate in deionized water to obtain potassium persulfate aqueous solution; add potassium persulfate aqueous solution and N,N,N',N'-tetramethylethylenediamine to pre-cooled mixed solution IV to obtain precursor solution II;

[0019] ③ Place the precursor liquid II into a mold containing the photothermal responsive hydrogel matrix I, and then place it in a vacuum environment for a period of time to react. Demold the hydrogel to obtain a colloidal mixture.

[0020] ④ The colloidal mixture was immersed in deionized water and dialyzed to remove unreacted substances, resulting in a photothermal responsive flexible bilayer hydrogel incorporating polyacid salts.

[0021] A photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts is used as a photothermal information acquisition and encryption device material that exhibits ultraviolet-responsive color change and photothermal-responsive deformation.

[0022] Principle of this invention:

[0023] This invention utilizes nucleophilic substitution between acryloyl chloride and β-cyclodextrin to obtain acylated β-cyclodextrin. Thermosensitive monomer poly(N-isopropylacrylamide) and acylated β-cyclodextrin form the hydrogel framework. Photothermal multi-walled carbon nanotubes are incorporated as the photothermal responsive layer of the hydrogel, and ammonium molybdate tetrahydrate is incorporated as the color-changing layer. The two hydrogel layers are bonded together by hydrogen bonds to prepare a bilayer hydrogel information compilation robot. Under initial conditions (<20℃ and no UV irradiation), the upper layer of the gel loaded with ammonium molybdate tetrahydrate is transparent, while the lower layer is black due to the multi-walled carbon nanotubes. At this point, UV irradiation causes the upper layer to change color, but the lower layer remains black, interfering with the color change and preventing normal information recognition. Heating the gel causes a phase transition due to the hydrophilic monomer in the upper layer, resulting in a color change from black to gray, while the upper layer remains colored and maintains a certain degree of transparency, allowing normal information observation. Further heating above the phase transition temperature of the upper layer causes the transparency of the upper gel to decrease, making normal observation impossible. This enables the hydrogel robot to display, transmit, and conceal information.

[0024] Advantages of this invention:

[0025] I. The photothermal responsive bilayer hydrogel information compilation robot incorporating polyacid salts prepared in this invention uses host-guest crosslinking between β-cyclodextrin and isopropyl groups in poly-N-isopropylacrylamide to form a multi-network interpenetration, exhibiting excellent flexibility.

[0026] II. The photothermal responsive flexible bilayer hydrogel with polyacid salts prepared in this invention, with the addition of multi-walled carbon nanotubes and N-isopropylacrylamide, exhibits photothermal responsive deformation characteristics.

[0027] III. The polyacid salt-incorporated photothermal responsive flexible bilayer hydrogel information compilation robot prepared in this invention, with the addition of ammonium molybdate tetrahydrate, exhibits reversible ultraviolet-responsive color change characteristics.

[0028] IV. The polyacid salt-incorporated photothermal responsive flexible bilayer hydrogel information compilation robot prepared in this invention adopts a melt-cast bilayer structure and exhibits excellent response anisotropy.

[0029] V. The polyacid salt-incorporated photothermal responsive flexible bilayer hydrogel information compilation robot prepared in this invention has high porosity, which is conducive to the movement of free ions and exhibits sensitive signal response characteristics and response stability.

[0030] This invention provides a photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts. Attached Figure Description

[0031] Figure 1 This is a reaction mechanism diagram of step one in Example 1;

[0032] Figure 2 This is a reaction mechanism diagram of step two in Example 1;

[0033] Figure 3 The figures are infrared spectra. Figure a represents the infrared spectrum of β-cyclodextrin, and figure b represents the infrared spectrum of the acylated modified β-cyclodextrin obtained in step 4 of Example 1.

[0034] Figure 4 This is the 1H NMR spectrum of the acylated modified β-cyclodextrin obtained in step 1④ of Example 1;

[0035] Figure 5 This is a particle size distribution diagram of the multi-walled carbon nanotube dispersion obtained in step two ① of Example 1;

[0036] Figure 6 The figures are infrared spectra. Figure a represents the infrared spectrum of poly(N-isopropylacrylamide), figure b represents the infrared spectrum of the photothermal responsive hydrogel matrix I obtained in step two of Example 1, and figure c represents the infrared spectrum of the photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts obtained in step three of Example 1.

[0037] Figure 7 The figures are X-ray diffraction patterns. In the figure, a represents the X-ray diffraction curve of the photothermal responsive hydrogel matrix I obtained in step two of Example 1, and b represents the red X-ray diffraction pattern of the photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts obtained in step three of Example 1.

[0038] Figure 8 This is the differential scanning calorimetry spectrum of the information compilation robot of the photothermal responsive bilayer hydrogel incorporating polyacid salts obtained in step three of Example 1;

[0039] Figure 9This is a thermogravimetric analysis diagram of the photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts, obtained in step three of Example 1.

[0040] Figure 10 This is a scanning electron microscope image of the photothermal responsive bilayer hydrogel information compilation robot incorporating polyacid salts, obtained in step three of Example 1;

[0041] Figure 11 The rheological performance test diagram of the information compilation robot with photothermal response and polyacid salt incorporation obtained in step three of Example 1 is shown. In the figure, █ represents the storage modulus of the hydrogel and ● represents the loss modulus of the hydrogel.

[0042] Figure 12 This is a tensile stress-strain test result diagram of the information compilation robot with photothermal response and polyacid salt incorporation obtained in step three of Example 1.

[0043] Figure 13 This is a graph showing the weight change over time in the degradation test of the polyacid salt-incorporated photothermal responsive flexible bilayer hydrogel information compilation robot obtained in step three of Example 1;

[0044] Figure 14 The image shows the UV-Vis spectrum of the hydrogel matrix II prepared in the control example, where a is the spectral line of the hydrogel matrix II prepared in the control example after UV irradiation, and b is the spectral line of the hydrogel matrix II prepared in the control example without UV irradiation.

[0045] Figure 15 The image shows the actual effect of the color development / fading process of hydrogel matrix II prepared in the control example as a function of molybdenum ion concentration and ultraviolet light irradiation time.

[0046] Figure 16 This is a graph showing the change in absorbance of the hydrogel matrix II prepared in the control example as a function of molybdenum ion concentration and UV irradiation time during the color development process. In the graph, █ represents a molybdenum ion concentration of 1.00 mol / L, ● represents a molybdenum ion concentration of 0.75 mol / L, ▲ represents a molybdenum ion concentration of 0.50 mol / L, ▼ represents a molybdenum ion concentration of 0.25 mol / L, and ◆ represents a molybdenum ion concentration of 0 mol / L.

[0047] Figure 17 This is a graph showing the change in absorbance of hydrogel matrix II prepared in the control example after 60 s of UV irradiation followed by cessation of irradiation, as a function of molybdenum ion concentration and UV irradiation duration. In the graph, █ represents a molybdenum ion concentration of 1.00 mol / L, ● represents a molybdenum ion concentration of 0.75 mol / L, ▲ represents a molybdenum ion concentration of 0.50 mol / L, ▼ represents a molybdenum ion concentration of 0.25 mol / L, and ◆ represents a molybdenum ion concentration of 0 mol / L.

[0048] Figure 18 The graph shows the change in transparency of the hydrogel matrix II prepared in the control example as a function of temperature and time. In the graph, █ represents a temperature of 20℃, ● represents a temperature of 40℃, and ▲ represents a temperature of 60℃.

[0049] Figure 19 This is a graph showing the change of gel temperature with infrared irradiation time in the infrared response test of the information compilation robot obtained by the polyacid salt-incorporated photothermal responsive flexible bilayer hydrogel in step three of Example 1.

[0050] Figure 20 This is a schematic diagram of the information load and encryption control of the photothermal responsive bilayer hydrogel information compilation robot obtained by incorporating polyacid salts in step three of Example 1. Detailed Implementation

[0051] Specific Implementation Method 1: This implementation method describes a method for preparing a photothermal responsive bilayer hydrogel information compilation robot incorporating polyacid salts, specifically completed according to the following steps:

[0052] I. Preparation of acylated modified β-cyclodextrin:

[0053] ① Add β-cyclodextrin and potassium hydroxide to deionized water and stir magnetically for a period of time in a water bath at 0℃~4℃ to obtain mixed solution I;

[0054] ② Add acryloyl chloride dropwise to mixed solution I while maintaining magnetic stirring during the addition process to obtain mixed solution II;

[0055] ③ Heat the mixed solution II in a water bath and stir magnetically for a period of time, then concentrate it under vacuum using a rotary evaporator to obtain a concentrated solution;

[0056] ④ The concentrate was added dropwise into acetone to precipitate the precipitate. After being filtered under reduced pressure, the precipitate was washed with acetone, pre-frozen for a period of time, and then freeze-dried under vacuum for a period of time to obtain acylated modified β-cyclodextrin.

[0057] II. Preparation of photothermal responsive hydrogel matrix I:

[0058] ① Weigh out multi-walled carbon nanotubes and hexadecyltrimethylammonium bromide, dissolve them in deionized water, and sonicate for a period of time to obtain a multi-walled carbon nanotube dispersion;

[0059] ② Dissolve N-isopropylacrylamide, acylated modified β-cyclodextrin and N',N'-methylenebisacrylamide in deionized water, stir for a period of time, then add multi-walled carbon nanotube dispersion, continue stirring for a period of time, and then pre-cool in a -4℃ environment to obtain pre-cooled mixed solution Ⅲ.

[0060] ③ Dissolve potassium persulfate in deionized water to obtain potassium persulfate aqueous solution; add potassium persulfate aqueous solution and N,N,N',N'-tetramethylethylenediamine to pre-cooled mixed solution Ⅲ to obtain precursor solution Ⅰ;

[0061] ④ Add the precursor liquid I into the silicone mold and place it in a vacuum environment for a period of time to react, so as to obtain a mold carrying the photothermal responsive hydrogel matrix I;

[0062] III. Preparation of a bilayer hydrogel information compilation robot:

[0063] ① Dissolve N-isopropylacrylamide, acylated modified β-cyclodextrin and N',N'-methylenebisacrylamide in deionized water, stir for a period of time, add methacryloyloxyethyltrimethylammonium chloride dropwise, then add ammonium molybdate tetrahydrate, continue stirring until a homogeneous and transparent mixed solution is obtained, place it in a -4℃ environment for pre-cooling, and obtain the pre-cooled mixed solution IV.

[0064] ② Dissolve potassium persulfate in deionized water to obtain potassium persulfate aqueous solution; add potassium persulfate aqueous solution and N,N,N',N'-tetramethylethylenediamine to pre-cooled mixed solution IV to obtain precursor solution II;

[0065] ③ Place the precursor liquid II into a mold containing the photothermal responsive hydrogel matrix I, and then place it in a vacuum environment for a period of time to react. Demold the hydrogel to obtain a colloidal mixture.

[0066] ④ The colloidal mixture was immersed in deionized water and dialyzed to remove unreacted substances, resulting in a photothermal responsive flexible bilayer hydrogel incorporating polyacid salts.

[0067] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that: the mass ratio of β-cyclodextrin to potassium hydroxide in the mixed solution I described in step one ① is 1:(0.2~0.5); the mass fraction of potassium hydroxide in the mixed solution I described in step one ① is 2wt%~4wt%; the magnetic stirring speed in step one ① is 600r / min~1200r / min, and the magnetic stirring time is 5min~15min. Other steps are the same as in Specific Implementation Method One.

[0068] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in the following ways: the volume ratio of acryloyl chloride to mixed solution I in step one ② is (5mL~10mL):(120mL~130mL); the dropping rate in step one ② is 0.3mL / min~1.0mL / min; the magnetic stirring speed in step one ② is 600r / min~1200r / min; the heating and magnetic stirring temperature in step one ③ is 25℃~55℃, the stirring speed is 600r / min~1200r / min, and the stirring time is 4h~9h; the vacuum concentration temperature in step one ③ is 40℃~70℃, concentrating to 1 / 8~1 / 4 of the original volume. Other steps are the same as in Specific Implementation Method One or Two.

[0069] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in the following ways: The pre-freezing temperature in step one (④) is -20°C, and the pre-freezing time is 8 to 12 hours; the vacuum freeze-drying temperature in step one (④) is -40°C to -80°C, and the vacuum freeze-drying time is 24 to 48 hours; the mass ratio of multi-walled carbon nanotubes to hexadecyltrimethylammonium bromide in step two (①) is 1:(1 to 3); the mass ratio of multi-walled carbon nanotubes to deionized water in step two (①) is (20 mg to 40 mg): 10 mL; the ultrasonic power in step two (①) is 300 W to 500 W, and the ultrasonic time is 30 to 60 minutes. Other steps are the same as in Specific Implementation Methods One to Three.

[0070] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in the following ways: In step two ②, the mass ratio of N-isopropylacrylamide, N',N'-methylenebisacrylamide, and acylated modified β-cyclodextrin is (32.5–65):2:1; the stirring time in step two ② is 5–15 min, and the stirring speed is 1000 r / min; the mass-to-volume ratio of N-isopropylacrylamide, deionized water, and multi-walled carbon nanotube dispersion in step two ② is (0.5 g–0.7 g):(5 mL–10 mL):(5 mL–15 mL); and the pre-cooling time in step two ② is 40 min–60 min. Other steps are the same as in Specific Implementation Methods One to Four.

[0071] Specific Implementation Method Six: The difference between this implementation method and Specific Implementation Methods One to Five is that: the concentration of the potassium persulfate aqueous solution in step two ③ is 10 mg / mL to 30 mg / mL; the volume ratio of the potassium persulfate aqueous solution, N,N,N',N'-tetramethylethylenediamine, and the pre-cooled mixed solution III in step two ③ is 1 mL:(20 μL to 40 μL):(5 mL to 15 mL); and the standing reaction time in step two ④ is 24 h to 48 h.

[0072] The other steps are the same as those in Specific Implementation Methods 1 to 5.

[0073] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in the following ways: In step three①, the mass ratio of N-isopropylacrylamide, N',N'-methylenebisacrylamide, and acylated modified β-cyclodextrin is (32.5–65):2:1; the mass-to-volume ratio of N-isopropylacrylamide, deionized water, and methacryloyloxyethyltrimethylammonium chloride in step three① is (0.5 g–0.8 g):(5 mL–15 mL):(0.1 mL–0.5 mL); the concentration of ammonium molybdate tetrahydrate in the pre-cooled mixed solution IV in step three① is 0.25 mol / L–1.00 mol / L; the stirring speed in step three① is 1000 r / min, and the stirring time is 5 min–15 min; the pre-cooling time in step three① is 40 min–60 min. Other steps are the same as in Specific Implementation Methods One to Six.

[0074] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that: the concentration of the potassium persulfate aqueous solution in step three ② is 10 mg / mL to 30 mg / mL; the volume ratio of the potassium persulfate aqueous solution, N,N,N',N'-tetramethylethylenediamine, and the pre-cooled mixed solution IV in step three ② is 1 mL:(20 μL to 40 μL):(10 mL to 25 mL). The other steps are the same as in Specific Implementation Methods One to Seven.

[0075] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in the following ways: the volume ratio of precursor liquid II to precursor liquid I in step three ③ is (2mL~5mL):(2mL~5mL); the static reaction time in step three ③ is 24h~48h; the soaking and dialysis time in step three ④ is 48h~96h, with water changed every 12h, and the molecular weight cutoff of the dialysis bag is 3500~5000. Other steps are the same as in Specific Implementation Methods One to Eight.

[0076] Specific Implementation Method 10: This implementation method uses a photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts as a photothermal information acquisition encryption material that exhibits ultraviolet-responsive color change and photothermal-responsive deformation.

[0077] The beneficial effects of the present invention are verified using the following embodiments:

[0078] Example 1: A method for preparing a photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts, specifically completed according to the following steps:

[0079] I. Preparation of acylated modified β-cyclodextrin:

[0080] ① Add 10.0g of β-cyclodextrin and 3.0g of potassium hydroxide to 125mL of deionized water, and stir magnetically for 10min in a water bath at 0℃~4℃. The stirring speed is 1000r / min to obtain mixed solution I.

[0081] ② Add 7.2 mL of acryloyl chloride dropwise to mixed solution I at a rate of 0.5 mL / min, while maintaining magnetic stirring at a speed of 1000 r / min during the addition process, to obtain mixed solution II;

[0082] ③ Transfer the mixed solution II into a 40°C water bath and heat it with magnetic stirring for 8 hours at a speed of 1000 r / min. Then, use a rotary evaporator at 45°C to vacuum evaporate and concentrate it to 1 / 5 of the original volume to obtain the concentrated solution.

[0083] ④ The concentrate was added dropwise into acetone to precipitate the precipitate. After being filtered under reduced pressure, the precipitate was washed three times with acetone, pre-frozen for a period of time, and then freeze-dried under vacuum for a period of time to obtain acylated modified β-cyclodextrin.

[0084] The pre-freezing temperature mentioned in step 1, ④ is -20℃, and the pre-freezing time is 12 hours;

[0085] The vacuum freeze-drying temperature described in step 1, ④ is -80℃, and the vacuum freeze-drying time is 48 hours;

[0086] II. Preparation of photothermal responsive hydrogel matrix I:

[0087] ① Weigh 30 mg of multi-walled carbon nanotubes and 30 mg of cetyltrimethylammonium bromide and dissolve them in 10 mL of deionized water. Sonicate the solution for 60 min at an ultrasonic power of 400 W to obtain a multi-walled carbon nanotube dispersion.

[0088] ② Dissolve 0.65g N-isopropylacrylamide, 0.01g acylated modified β-cyclodextrin and 20mg N',N'-methylenebisacrylamide in 7mL of deionized water, stir at 1000r / min for 15min, then add multi-walled carbon nanotube dispersion, continue stirring at 1000r / min for 10min, and then pre-cool at -4℃ for 60min to obtain pre-cooled mixed solution Ⅲ;

[0089] ③ Dissolve 200 mg of potassium persulfate in 10 mL of deionized water to obtain a potassium persulfate aqueous solution with a concentration of 20 mg / mL; add 1 mL of the potassium persulfate aqueous solution with a concentration of 20 mg / mL and 30 μL of N,N,N',N'-tetramethylethylenediamine to the pre-cooled mixed solution III to obtain precursor solution I;

[0090] ④ Add 5 mL of precursor liquid I into a silicone mold with dimensions of 5 cm × 2 cm × 2 cm and place it in a vacuum environment for static reaction for 24 h to obtain a mold carrying photothermal responsive hydrogel matrix I.

[0091] III. Preparation of a bilayer hydrogel information compilation robot:

[0092] ① Dissolve 0.65g N-isopropylacrylamide, 0.01g acylated modified β-cyclodextrin and 20mg N',N'-methylenebisacrylamide in 10mL of deionized water. Stir at 1000r / min for 15min. Add 0.2mL of methacryloyloxyethyltrimethylammonium chloride dropwise, then add 0.01mol of ammonium molybdate tetrahydrate. Continue stirring until a homogeneous and transparent mixed solution is obtained. Pre-cool at -4℃ for 60min to obtain the pre-cooled mixed solution IV.

[0093] ② Dissolve 200 mg of potassium persulfate in 10 mL of deionized water to obtain a potassium persulfate aqueous solution with a concentration of 20 mg / mL; add 1 mL of the potassium persulfate aqueous solution with a concentration of 20 mg / mL and 30 μL of N,N,N',N'-tetramethylethylenediamine to the pre-cooled mixed solution IV to obtain precursor solution II;

[0094] ③ Place 5 mL of precursor liquid II into a mold containing photothermal responsive hydrogel matrix I, and then allow it to stand under vacuum for 48 h. Demold the hydrogel to obtain a colloidal mixture.

[0095] ④ The colloidal mixture was immersed and dialyzed in 200mL of deionized water. The water was changed every 12 hours and repeated 6 times to remove unreacted substances, and a photothermal responsive flexible bilayer hydrogel incorporating polyacid salts was obtained.

[0096] The molecular weight cutoff of the dialysis bag mentioned in step 3④ is 5000.

[0097] Figure 1 This is a reaction mechanism diagram of step one in Example 1;

[0098] pass Figure 1 It can be seen that β-cyclodextrin undergoes an acylation reaction with acryloyl chloride under the action of potassium hydroxide alkaline solution, resulting in acylated β-cyclodextrin.

[0099] Figure 2 This is a reaction mechanism diagram of step two in Example 1;

[0100] from Figure 2 It can be seen that acylated β-cyclodextrin and N-isopropylacrylamide form a gel host network skeleton through free radical polymerization and host-guest crosslinking. Hydrogel matrix I and hydrogel matrix II are prepared by incorporating multi-walled carbon nanotubes or ammonium molybdate tetrahydrate into the gel skeleton, respectively. Flexible bilayer hydrogel information compilation robot material is obtained by casting the reaction solution and hydrogen bonding.

[0101] Figure 3 The figures are infrared spectra. Figure a represents the infrared spectrum of β-cyclodextrin, and figure b represents the infrared spectrum of the acylated modified β-cyclodextrin obtained in step 4 of Example 1.

[0102] Depend on Figure 3 It can be seen that at 3400cm -1 A vibrational absorption peak for -OH appears at 2920 cm⁻¹. -1 The -CH stretching vibration absorbing bee appears at 1150cm. -1 and 1180cm -1 The peaks at these locations represent the absorption peaks of the CO and COC stretching vibrations within the β-CD cavity, respectively. Compare the β-CD spectrum with the ACD spectrum (…). Figure 3 As can be seen from spectral line b), ACD still retains the original cavity structure of β-CD, and at 1720 cm⁻¹ -1 1210cm -1 808cm -1 The addition of C=O, CO, and C=C absorption vibration peaks at the wavenumber indicates that the carbon-carbon double bond was successfully introduced into β-CD via acetylation.

[0103] Figure 4 This is the 1H NMR spectrum of the acylated modified β-cyclodextrin obtained in step 1④ of Example 1;

[0104] Depend on Figure 4 It can be seen that acryloyl chloride preferentially reacts with the primary hydroxyl group at the 6th substitution position on β-CD ( Figure 4A nucleophilic substitution reaction was carried out in d′ to prepare acetylated β-CD. In addition, the peak area integral results showed that the unit cyclodextrin grafted with about one C=C structure, that is, the ACD gel precursor containing one carbon-carbon double bond was obtained, indicating that the acetyl-modified β-cyclodextrin was successfully prepared.

[0105] Figure 5 This is a particle size distribution diagram of the multi-walled carbon nanotube dispersion obtained in step two ① of Example 1;

[0106] Depend on Figure 5 It can be seen that the particle size distribution range of multi-walled carbon nanotubes is 14 nm to 5.55 μm, the average particle size is 934.867 ± 93.613 nm, and the PDI value is 0.690 ± 0.00495, indicating that the sample is well dispersed.

[0107] Figure 6 The figures are infrared spectra. Figure a represents the infrared spectrum of poly(N-isopropylacrylamide), figure b represents the infrared spectrum of the photothermal responsive hydrogel matrix I obtained in step two of Example 1, and figure c represents the infrared spectrum of the photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts obtained in step three of Example 1.

[0108] Depend on Figure 6 It can be seen that: in spectral line a, 3290 cm⁻¹ -1 The peak at 2980 cm⁻¹ represents the stretching vibration of the NH bond in a free amino group. -1 and 2930cm -1 These represent the CH stretching vibration peaks in the methyl and methylene groups on PNIPAM, respectively, at 1640 cm⁻¹. -1 and 1450cm -1 The peak at 1080 cm⁻¹ represents the C=O vibration of the amide bond. Comparing spectra b and c, the main characteristic peaks of poly(N-isopropylacrylamide) both appear in spectra b and c, indicating that the hydrogel matrix I obtained in step two of Example 1 and the flexible bilayer hydrogel material obtained in step three of Example 1 both possess similar characteristic functional group infrared spectral features to poly(N-isopropylacrylamide), and both retain the poly(N-isopropylacrylamide) skeleton. Furthermore, spectra b and c show similar peaks at 1080 cm⁻¹. -1 The presence of an antisymmetric stretching vibration peak in the oxygen bridge of β-cyclodextrin is consistent with the literature, indicating that a flexible bilayer hydrogel compiler robot has been successfully prepared.

[0109] Figure 7 The figures are X-ray diffraction patterns. In the figure, a represents the X-ray diffraction curve of the photothermal responsive hydrogel matrix I obtained in step two of Example 1, and b represents the red X-ray diffraction pattern of the photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts obtained in step three of Example 1.

[0110] Depend on Figure 7 It can be seen that the two broad diffraction peaks at 8° and 19° in hydrogel matrix I are characteristic peaks of the amorphous structure of poly-N-isopropylacrylamide, while the broad diffraction peak at 2θ = 12° is presumably due to β-cyclodextrin. In spectrum b, the diffraction peaks at 2θ = 8°, 2θ = 12°, and 2θ = 19° disappear, and two weak broad diffraction peaks appear at 2θ = 10° and 2θ = 27°. The X-ray diffraction patterns of the measured materials show broad diffuse scattering peaks, indicating that they possess an amorphous structure.

[0111] Figure 8 This is the differential scanning calorimetry spectrum of the information compilation robot of the photothermal responsive bilayer hydrogel incorporating polyacid salts obtained in step three of Example 1;

[0112] Depend on Figure 8 It can be seen that the water-bound evaporating gel robot material experiences its first mass loss at 25℃ to about 125℃, with a loss of about 3%; a significant second mass loss begins at 245℃ and ends at 400℃. During this process, the interaction between the cyclodextrin host and the methyl guest in poly(N-isopropylacrylamide) inside the gel is overcome, and the carbon-carbon single bonds formed by free radical polymerization crosslinking are broken, causing the gel network structure to degrade.

[0113] Figure 9 This is a thermogravimetric analysis diagram of the photothermal responsive flexible bilayer hydrogel information compilation robot incorporating polyacid salts, obtained in step three of Example 1.

[0114] As shown in the figure, the flexible bilayer hydrogel robot material exhibits two distinct endothermic peaks at 265℃ and 396℃. The endothermic peak at 265℃ is presumably due to the endothermic effect of overcoming the host-guest interaction, while the endothermic peak at 396℃ is due to the endothermic effect of the breakage of C-C bonds in the gel skeleton.

[0115] Figure 10 This is a scanning electron microscope image of the photothermal responsive bilayer hydrogel information compilation robot incorporating polyacid salts, obtained in step three of Example 1;

[0116] Depend on Figure 10 The microstructure of the bilayer hydrogel robotic material, magnified 30x, 100x, and 500x, shows that both types of hydrogels are multi-level, three-dimensional network structures with tightly connected pores, indicating successful preparation of the target hydrogel. The bilayer hydrogel exhibits distinct layer boundaries, forming a denser three-dimensional network structure. The incorporation of multi-walled carbon nanotubes and the electrostatic interaction between molybdate ions and methacryloyloxyethyltrimethylammonium chloride increase the crosslinking sites of the gel chains, thus enhancing the degree of crosslinking and making the network structure more compact.

[0117] Figure 11The rheological performance test diagram of the information compilation robot with photothermal response and polyacid salt incorporation obtained in step three of Example 1 is shown. In the figure, █ represents the storage modulus of the hydrogel and ● represents the loss modulus of the hydrogel.

[0118] Depend on Figure 11 It can be seen that the flexible bilayer hydrogel robotic material exhibits elastic behavior greater than viscous behavior, indicating the successful preparation of the target hydrogel. Furthermore, the host-guest interaction physical cross-linking strategy causes the bilayer hydrogel robotic material to show a significant increasing trend in storage modulus and loss modulus with increasing angular frequency, resulting in chain aggregation.

[0119] Figure 12 This is a tensile stress-strain test result diagram of the information compilation robot with photothermal response and polyacid salt incorporation obtained in step three of Example 1.

[0120] like Figure 12 As shown, the maximum stress and maximum tensile strain of the flexible bilayer hydrogel compilation robot material increased to 42 kPa and 1300%, respectively, and the toughness value was significantly improved to 26.15 MPa, proving that the host-guest interaction between acylated modified β-cyclodextrin and N-isopropylacrylamide endows the hydrogel with good tensile properties.

[0121] Figure 13 This is a graph showing the weight change over time in the degradation test of the polyacid salt-incorporated photothermal responsive flexible bilayer hydrogel information compilation robot obtained in step three of Example 1;

[0122] Depend on Figure 13 It can be seen that after the bilayer hydrogel material of the present invention is immersed in 10 mL of 0.01 M PBS solution for 30 days, its quality retention rate is still higher than 95%, indicating that the target flexible bilayer hydrogel robot does not undergo significant degradation in the external environment, has good stability, and can be used as an in vitro intelligent robot for a long time.

[0123] Comparative example: Hydrogel matrix II was prepared according to the following steps:

[0124] I. Preparation of a bilayer hydrogel information compilation robot:

[0125] ① Dissolve 0.65g N-isopropylacrylamide, 0.01g acylated modified β-cyclodextrin and 20mg N',N'-methylenebisacrylamide in 10mL of deionized water. Stir at 1000r / min for 15min. Add 0.2mL of methacryloyloxyethyltrimethylammonium chloride dropwise, then add 0.01mol of ammonium molybdate tetrahydrate. Continue stirring until a homogeneous and transparent mixed solution is obtained. Pre-cool at -4℃ for 60min to obtain pre-cooled mixed solution I.

[0126] ② Dissolve 200 mg of potassium persulfate in 10 mL of deionized water to obtain a potassium persulfate aqueous solution with a concentration of 20 mg / mL; add 1 mL of the potassium persulfate aqueous solution with a concentration of 20 mg / mL and 30 μL of N,N,N',N'-tetramethylethylenediamine to the pre-cooled mixed solution I to obtain precursor solution II;

[0127] ③ Place 5 mL of precursor liquid II into the mold, and then place it in a vacuum environment for static reaction for 48 h. Demold the hydrogel to obtain hydrogel matrix II.

[0128] Figure 14 The image shows the UV-Vis spectrum of the hydrogel matrix II prepared in the control example, where a is the spectral line of the hydrogel matrix II prepared in the control example after UV irradiation, and b is the spectral line of the hydrogel matrix II prepared in the control example without UV irradiation.

[0129] As can be seen from spectra a and b, the unirradiated hydrogel matrix II spectrum has no obvious absorption peak, while the spectrum after UV irradiation shows an obvious absorption peak with the maximum absorption peak at 730 nm, and the gel turns blue, indicating that hydrogel matrix II was successfully prepared.

[0130] Figure 15 The image shows the actual effect of the color development / fading process of hydrogel matrix II prepared in the control example as a function of molybdenum ion concentration and ultraviolet light irradiation time.

[0131] Depend on Figure 15 It can be seen that as the concentration of molybdenum ions increases, the gel staining becomes faster after ultraviolet irradiation, and the staining is more stable and the fading time is slower after dark treatment.

[0132] Figure 16 This is a graph showing the change in absorbance of the hydrogel matrix II prepared in the control example as a function of molybdenum ion concentration and UV irradiation time during the color development process. In the graph, █ represents a molybdenum ion concentration of 1.00 mol / L, ● represents a molybdenum ion concentration of 0.75 mol / L, ▲ represents a molybdenum ion concentration of 0.50 mol / L, ▼ represents a molybdenum ion concentration of 0.25 mol / L, and ◆ represents a molybdenum ion concentration of 0 mol / L.

[0133] Figure 17 This is a graph showing the change in absorbance of hydrogel matrix II prepared in the control example after 60 s of UV irradiation followed by cessation of irradiation, as a function of molybdenum ion concentration and UV irradiation duration. In the graph, █ represents a molybdenum ion concentration of 1.00 mol / L, ● represents a molybdenum ion concentration of 0.75 mol / L, ▲ represents a molybdenum ion concentration of 0.50 mol / L, ▼ represents a molybdenum ion concentration of 0.25 mol / L, and ◆ represents a molybdenum ion concentration of 0 mol / L.

[0134] Figure 16 and Figure 17 The graph shows the changes in absorbance of the hydrogel matrix II prepared in the control example during the color development (fading) process as a function of molybdenum ion concentration and UV irradiation (darkness) treatment time. It can be seen that the absorbance of the gel increases with increasing molybdenum ion concentration in the first 30 seconds of irradiation. With continued irradiation, the absorbance of the gel sample with a molybdenum ion concentration of 1.00 mol / L is the highest, and the detection accuracy of the microplate reader decreases. At this point, irradiation is stopped, and the sample is placed under ambient conditions to observe the fading of the gel. When the molybdenum ion concentration is below 0.50 mol / L, although the gel exhibits good color development behavior, the staining is unstable, and the gel fades significantly after about 30 minutes of dark chamber treatment. When the molybdenum ion concentration is 0.75 mol / L and 1.00 mol / L, the gel staining can be maintained for more than 3 hours, indicating that appropriately increasing the molybdenum ion concentration can enhance the color development stability of the gel.

[0135] Figure 18 The graph shows the change in transparency of the hydrogel matrix II prepared in the control example as a function of temperature and time. In the graph, █ represents a temperature of 20℃, ● represents a temperature of 40℃, and ▲ represents a temperature of 60℃.

[0136] When the water bath temperature is between 20℃ and 40℃, ultraviolet light irradiation induces the reduction and color development of molybdenum ions within gel matrix II, resulting in a significant decrease in gel transmittance of approximately 15%. Upon removal of light, the gel fades, and its transparency reaches approximately 90%. Furthermore, during 10 cycles of irradiation, the transparency error remains within 3%, indicating good stability of the photoresponsive color development. However, when the gel temperature reaches 60℃, exceeding the phase transition temperature, the gel network transforms to a hydrophobic state, causing an overall decrease in gel transmittance. Therefore, during cyclic irradiation, its transmittance shows no significant change. These conclusions provide a basis for asynchronous temperature response in the subsequent information encryption of flexible bilayer robots.

[0137] Figure 19 This is a graph showing the change of gel temperature with infrared irradiation time in the infrared response test of the information compilation robot obtained by the polyacid salt-incorporated photothermal responsive flexible bilayer hydrogel in step three of Example 1.

[0138] Depend on Figure 19 It can be seen that the hydrogel material of the present invention exhibits significant temperature changes after infrared light irradiation. The temperature increases by 8.29°C in the first 300 seconds, with a relatively fast heating rate. The heating rate slows down from 300 to 600 seconds. After irradiation for 600 seconds, the gel temperature does not show significant changes, indicating good photothermal properties.

[0139] Figure 20 This is a schematic diagram of the information load and encryption control of the photothermal responsive bilayer hydrogel information compilation robot obtained by incorporating polyacid salts in step three of Example 1.

[0140] As shown in the figure, under initial conditions (temperature < 20℃ and no UV irradiation), the upper layer of the gel is transparent, while the lower layer is black due to multi-walled carbon nanotubes. At this point, UV irradiation causes the hydrogel matrix II to change color, but the lower hydrogel matrix I interferes with the color change, making it impossible to properly identify the information. Heating the gel then causes a temperature shift between the upper and lower layers due to the presence of the hydrophilic monomer methacryloyloxyethyltrimethylammonium chloride in the hydrogel matrix II. The lower hydrogel matrix I undergoes a phase transition upon heating, changing its color from black to gray, while the upper layer remains colored and maintains a certain degree of transparency, allowing for normal information observation. Further heating above the phase transition temperature of the hydrogel matrix I causes a decrease in the transparency of the upper gel, making normal observation impossible. However, by controlling the temperature to restore the gel to its initial state, reversible information compilation can be achieved, allowing it to participate in a new round of information compilation. This enables the formation of images and text on the hydrogel surface, utilizing the photothermal response characteristics of images or text to achieve the flexible bilayer hydrogel's ability to display, transmit, and hide human information.

Claims

1. A method for preparing a polyacid salt-incorporated photothermal response flexible double-layer hydrogel information compiling robot, characterized in that The preparation method is specifically completed according to the following steps: I. Preparation of acylated modified β-cyclodextrin: ①, β-cyclodextrin and potassium hydroxide are added to deionized water, and magnetic stirring is carried out at 0-4°C water bath for a period of time to obtain mixed solution I; ②, acryloyl chloride is added dropwise to mixed solution I, and magnetic stirring is maintained during the dropwise addition process to obtain mixed solution II; ③, mixed solution II is heated in a water bath and magnetically stirred for a period of time, and then vacuum concentrated by a rotary evaporator to obtain a concentrated solution; ④, the concentrated solution is added dropwise into acetone for precipitation, and then filtered under reduced pressure; the precipitate is washed with acetone, pre-cooled for a period of time, and then vacuum freeze-dried for a period of time to obtain acylated modified β-cyclodextrin; II. Preparation of photothermal responsive hydrogel matrix I: ①, multi-walled carbon nanotubes and cetyltrimethylammonium bromide are dissolved in deionized water, and ultrasonic is carried out for a period of time to obtain a multi-walled carbon nanotube dispersion; ②, N-isopropyl acrylamide, acylated modified β-cyclodextrin and N', N'-methylene bisacrylamide are dissolved in deionized water, stirred for a period of time, then the multi-walled carbon nanotube dispersion is added, and stirred for a period of time, and then pre-cooled in a-4°C environment to obtain a pre-cooled mixed solution III; ③, potassium persulfate is dissolved in deionized water to obtain a potassium persulfate aqueous solution; the potassium persulfate aqueous solution and N, N, N', N'-tetramethyl ethylenediamine are added to the pre-cooled mixed solution III to obtain a precursor solution I; ④, the precursor solution I is added to a silica gel mold and placed in a vacuum environment for a period of time to obtain a mold loaded with photothermal responsive hydrogel matrix I; III. Preparation of double-layer hydrogel information compiling robot: ①, N-isopropyl acrylamide, acylated modified β-cyclodextrin and N', N'-methylene bisacrylamide are dissolved in deionized water, stirred for a period of time, then methyl acryloyloxyethyl trimethyl ammonium chloride is added dropwise, and then ammonium molybdate tetrahydrate is added, and the stirring is continued until a uniform transparent mixed solution is obtained, which is pre-cooled in a-4°C environment to obtain a pre-cooled mixed solution IV; ②, potassium persulfate is dissolved in deionized water to obtain a potassium persulfate aqueous solution; the potassium persulfate aqueous solution and N, N, N', N'-tetramethyl ethylenediamine are added to the pre-cooled mixed solution IV to obtain a precursor solution II; ③, the precursor solution II is placed in the mold loaded with photothermal responsive hydrogel matrix I, and then placed in a vacuum environment for a period of time to react, and the hydrogel is demolded to obtain a colloidal mixture; ④, the colloidal mixture is soaked and dialyzed in deionized water to remove unreacted substances to obtain a multi-acid salt doped photothermal responsive flexible double-layer hydrogel information compiling robot.

2. The method for preparing a polyacid salt-incorporated photothermal response flexible double-layer hydrogel information compiling robot according to claim 1, characterized in that In step 1 ①, the mass ratio of β-cyclodextrin to potassium hydroxide in the mixed solution I is 1:(0.2-0.5); the mass fraction of potassium hydroxide in the mixed solution I in step 1 ① is 2wt%-4wt%; the speed of magnetic stirring in step 1 ① is 600r / min-1200r / min, and the time of magnetic stirring in step 1 ① is 5min-15min.

3. The method of claim 1, wherein the method is characterized by The volume ratio of acryloyl chloride to mixed solution I in step one ② is (5 mL-10 mL):(120 mL-130 mL); the dropping speed in step one ② is 0.3 mL / min-1.0 mL / min; the speed of magnetic stirring in step one ② is 600 r / min-1200 r / min; the temperature of heating and magnetic stirring in step one ③ is 25 ℃-55 ℃, the stirring speed is 600 r / min-1200 r / min, and the stirring time is 4 h-9 h; the temperature of vacuum concentration in step one ③ is 40 ℃-70 ℃, and the concentration is to 1 / 8-1 / 4 of the original volume.

4. The method of claim 1, wherein the method is characterized by The pre-freezing temperature in step one ④ is -20 ℃, and the pre-freezing time is 8 h-12 h; the temperature of vacuum freeze-drying in step one ④ is -40 ℃--80 ℃, and the vacuum freeze-drying time is 24 h-48 h; the mass ratio of multi-walled carbon nanotubes to cetyltrimethylammonium bromide in step two ① is 1:(1-3); the mass of multi-walled carbon nanotubes to the volume of deionized water in step two ① is (20 mg-40 mg):10 mL; the ultrasonic power in step two ① is 300 W-500 W, and the ultrasonic time is 30 min-60 min.

5. The method of claim 1, wherein the method is characterized by The mass ratio of N-isopropyl acrylamide, N',N'-methylene bisacrylamide and acylated modified β-cyclodextrin in step two ② is (32.5-65):2:1; the stirring time in step two ② is 5 min-15 min, and the stirring speed is 1000 r / min; the mass of N-isopropyl acrylamide, the mass of deionized water and the mass of multi-walled carbon nanotube dispersion in step two ② is (0.5 g-0.7 g):(5 mL-10 mL):(5 mL-15 mL); the pre-cooling time in step two ② is 40 min-60 min.

6. The method of claim 1, wherein the method is characterized by The concentration of potassium persulfate aqueous solution in step two ③ is 10 mg / mL-30 mg / mL; the volume ratio of potassium persulfate aqueous solution, N,N,N',N'-tetramethyl ethylenediamine and pre-cooled mixed solution III in step two ③ is 1 mL:(20 μL-40 μL):(5 mL-15 mL); the standing reaction time in step two ④ is 24 h-48 h.

7. The method of claim 1, wherein the method is characterized by The mass ratio of N-isopropylacrylamide, N', N'-methylene bisacrylamide and acylated modified β-cyclodextrin described in step three ① is (32.5-65):2:1; the mass-volume ratio of N-isopropylacrylamide, deionized water and methacryloyloxyethyl trimethylammonium chloride described in step three ① is (0.5g-0.8g):(5mL-15mL):(0.1mL-0.5mL); the concentration of ammonium molybdate tetrahydrate in the pre-cooled mixed solution IV described in step three ① is 0.25mol / L-1.00mol / L; the stirring speed described in step three ① is 1000r / min, and the stirring time is 5min-15min; the pre-cooling time described in step three ① is 40min-60min.

8. The method of claim 1, wherein the method is characterized by The concentration of the potassium persulfate aqueous solution described in step three ② is 10mg / mL-30mg / mL; the volume ratio of the potassium persulfate aqueous solution, N,N,N',N'-tetramethyl ethylenediamine and the pre-cooled mixed solution IV described in step three ② is 1mL:(20μL-40μL):(10mL-25mL).

9. The method of claim 1, wherein the method is characterized by The volume ratio of the precursor liquid II to the precursor liquid I described in step three ③ is (2mL-5mL):(2mL-5mL); the standing reaction time described in step three ③ is 24h-48h; the immersion dialysis time described in step three ④ is 48h-96h, and the water is changed every 12h, and the molecular weight cut-off of the dialysis bag is 3500-5000. 10.The application of the polyacid salt incorporated photothermal responsive flexible double-layer hydrogel information compiling robot prepared by the preparation method of claim 1. The polyacid salt incorporated photo-thermal response flexible double-layer hydrogel information compiling robot is used as a photo-thermal information acquisition encrypter material which responds to ultraviolet and changes color and deforms in photo-thermal response.

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