A super-tough photothermal energy storage three-dimensional network polymer and its preparation method

Abstract

The present invention discloses a super-tough photothermal energy storage three-dimensional network polymer and a preparation method thereof. First, an isocyanate group-terminated prepolymer is prepared by reacting a diisocyanate and a flexible long-chain diol. Then, the prepolymer is reacted with a dioxime-based monomer to prepare a linear oligomer polymer with photothermal conversion function and phase change group blocks. Finally, the linear oligomer polymer is cured by a trifunctional triol to form a three-dimensional network polymer. Due to its own cross-linked stable structure, it can effectively solve the problem of poor toughness of the material, solve problems such as structural damage during flexible wearing, achieve a long service life, improve the durability of the material, and can prepare a photothermal energy storage and super-tough polymer material with good properties, realizing continuous power supply and wearing comfort of intelligent wearables.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of photothermal energy storage polymers, and particularly relates to a super-tough photothermal energy storage three-dimensional network polymer and a preparation method thereof. Background Art

[0002] With the improvement of living standards and quality, self-powered intelligent flexible wearables are a key development direction in future technology. As a clean energy source, solar energy has the advantages of being readily available and inexhaustible, and has become one of the solutions to global problems such as the earth's energy crisis, environmental pollution, and the greenhouse effect. It is an ideal energy source for flexible wearables. However, due to the low energy density of solar radiation and the uncertainty of the natural environment, the utilization rate of solar energy photothermal conversion has also been greatly limited. Therefore, it is necessary to find an energy storage device that can solve the shortcoming of the mismatch between solar energy in time and space and achieve stable energy supply.

[0003] At present, thermal energy storage mainly includes chemical heat storage, sensible heat storage, and phase change heat storage. Among them, phase change refers to the reversible phenomenon that when the temperature reaches the phase transition temperature of the solid-liquid, liquid-gas, and solid-gas phases of the material, the material absorbs or releases a large amount of latent heat due to physical phase changes, and the ambient temperature can be maintained unchanged for a period of time during this process, so as to ensure that the temperature does not rise or fall further. Therefore, phase change materials have also been applied to solve the problem of the mismatch between solar energy in time and space due to their advantages of high energy storage density, strong energy storage capacity, small temperature change, low price, and environmental friendliness, and the application of solar energy photothermal utilization has been promoted.

[0004] However, in practical applications, only about 40% of the infrared band in solar radiation can directly produce a thermal effect, while the visible light band, which accounts for about 50% of solar radiation, does not have a thermal effect and is difficult to directly absorb and utilize. It is necessary to rely on light trapping or photothermal conversion materials to achieve the conversion and efficient thermal utilization of visible light. In order to improve the photothermal conversion efficiency of the system, light conversion materials will be added: selective absorption carbon black, cobalt coatings, metals, metal oxides, metal sulfides, semiconductors, organic pigments, organic dyes, etc. in the photothermal conversion system of photothermal technology. Therefore, the performance of the composite material will be greatly affected when constructing a photothermal energy storage system.

[0005] Therefore, there is an urgent need for a photothermal energy storage polymer and a preparation process that can integrate functions such as photothermal conversion, thermal energy storage, flexibility, and stretchability. Summary of the Invention

[0006] To solve the problems existing in the prior art, the present invention provides a super-tough photo-thermal energy storage three-dimensional network polymer and its preparation method, which is a polymer composed of a phase change group block and photo-thermal conversion energy storage. By molecular synthesis, the photo-thermal conversion functional group and the phase change functional group are block-copolymerized onto the molecular chain, so as to achieve the dual functions of photo-thermal energy storage and super toughness, and can prepare a polymer material with good photo-thermal energy storage and super toughness, realizing the continuous power supply and wearing comfort of intelligent wear, and solving the problems mentioned in the above background technology.

[0007] To achieve the above object, the present invention provides the following technical solution: A super-tough photo-thermal energy storage three-dimensional network polymer is first prepared by reacting a diisocyanate with a flexible long-chain diol to prepare an isocyanate-bond-terminated prepolymer, and then the prepolymer is reacted with a dioxime-based monomer to prepare a linear oligomer polymer with photo-thermal conversion function and phase change group block. Finally, the linear oligomer polymer is cured by a trifunctional triol to form a three-dimensional network polymer, and its molecular structure is

[0008]

[0009]

[0010] In addition, to achieve the above object, the present invention also provides the following technical solution: A preparation method of a super-tough photo-thermal energy storage three-dimensional network polymer, comprising the following steps:

[0011] S1. Under the protection of high-purity nitrogen, the flexible long-chain diol is vacuum-dried for 2-12 h and then added to the diisocyanate, and reacted under the condition of uniform stirring to obtain an -NCO-terminated prepolymer;

[0012] S2. Add p-benzoquinone dioxime to an organic solvent and stir to dissolve it to obtain a p-benzoquinone dioxime organic solution, and then drop the p-benzoquinone dioxime organic solution into the -NCO-terminated prepolymer and heat and reflux with stirring to react to obtain a linear oligomer polymer with photo-thermal conversion function and phase change group block;

[0013] S3. Add triethanolamine to an organic solvent and stir to dissolve it to obtain a triethanolamine organic solution, and then add the triethanolamine organic solution to the linear oligomer polymer, and stir to obtain a uniform dark brown liquid;

[0014] S4. Pour the uniform dark brown liquid into a polytetrafluoroethylene mold and place it in a vacuum oven at 30-50 °C to heat for 2-4 hours, and then raise the temperature for curing to obtain a super-tough photo-thermal energy storage three-dimensional network polymer.

[0015] Preferably, the molecular weight of the flexible long-chain diol is 4000-10000, and the flexible long-chain diol is polyethylene glycol PEG, polybutylene glycol PTMG or a mixture of the two.

[0016] Preferably, in step S1, the reaction under the condition of uniform stirring is specifically: reflux reaction at 40-100 °C for 3-12 h.

[0017] Preferably, the molar ratio of the flexible long-chain diol to the diisocyanate is 1:2.

[0018] Preferably, the diisocyanate is toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI) or hexamethylene diisocyanate (HDI); the organic solvent is N,N-dimethylformamide, tetrahydrofuran, N,N-dimethylacetamide or dimethyl sulfoxide.

[0019] Preferably, in step S2, the heating and reflux stirring reaction is specifically: under the protection of high-purity nitrogen, reflux stirring reaction at a temperature of 40-120 °C for 2-6 h.

[0020] Preferably, the molar ratio of the flexible long-chain diol to p-benzoquinone dioxime is 1:1.

[0021] Preferably, in step S3, the molar ratio of triethanolamine added to the flexible long-chain diol is 1-2:1, and the stirring time is 10-30 min.

[0022] Preferably, in step S4, the further temperature increase and curing is specifically: further increase the temperature to 60-120 °C for curing treatment for 2-4 h.

[0023] The beneficial effects of the present invention are as follows:

[0024] 1) The present invention prepares a phase change functional group block backbone chain structure with a flexible molecular chain structure through molecular structure design, endowing the polymer material with a phase change energy storage function.

[0025] 2) The present invention introduces a p-benzoquinone structure with light absorption function and photothermal conversion function into the polymer molecular chain through chemical covalent bond action. Due to the limitation of the molecular chain structure and chemical covalent bond, problems such as material migration and interfacial defects caused by phase separation in the composite material can be effectively solved. The organic combination of the photothermal conversion functional group, the phase change functional group and the three-dimensional crosslinked network endows the polymer material with the ability to absorb about 90% of the energy of infrared light and visible light in solar radiation, the ability of the polymer material to store light energy as heat energy, and the characteristics such as the ultra-long fracture tensile strength of the polymer.

[0026] 3) The preparation method of the super-tough photothermal energy storage polymer of the present invention can effectively solve the problem of poor toughness of the material due to its own crosslinked stable structure, solve problems such as structural damage during flexible wearing, realize a long service life, and improve material durability. Description of the Drawings

[0027] Figure 1 Schematic diagram of the synthesis reaction formula of sample Y1 in the embodiment;

[0028] Figure 2 Schematic diagram of sample Y1 in the embodiment;

[0029] Figure 3 Schematic diagram of the infrared spectrum of sample Y1 in the embodiment;

[0030] Figure 4 XRD curve of sample Y1 in the embodiment;

[0031] Figure 5 DSC heating and cooling cycle curve of sample Y1 in the embodiment;

[0032] Figure 6 Stress-strain curve of sample Y1 in the embodiment;

[0033] Figure 7 Photothermal conversion curve of sample Y1 in the embodiment;

[0034] Figure 8 Energy storage curve of sample Y1 in the embodiment. Detailed implementation manners

[0035] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0036] The present invention adopts solution polycondensation reaction and prepares the final product by a one-pot method. It is a polyurethane synthesis method that absorbs light and generates heat through an oxime group, realizes photothermal conversion, and then realizes the functions of heat storage and release through a phase change process.

[0037] A super-tough photothermal energy storage three-dimensional network polymer is first prepared by reacting a diisocyanate and a flexible long-chain diol to prepare an isocyanate bond-capped prepolymer, and then reacting the prepolymer with a binary oxime monomer to prepare a linear oligomer polymer with photothermal conversion function and phase change group segments. Finally, a three-functional triol is used as a crosslinking agent to cure the linear oligomer polymer to form a three-dimensional network polymer.

[0038] The three-dimensional network established by the present invention is formed by reacting an excessive bifunctional diisocyanate, a long-chain diol, and a di-oxime-based monomer to form a linear prepolymer, and then adding a trifunctional triol to react with the remaining isocyanate functional groups on the excessive diisocyanate to form a three-dimensional network structure with adjustable crosslinking density. And the existence of the three-dimensional structure endows the material with better mechanical properties.

[0039] Its three-dimensional network polymer molecular structure is:

[0040]

[0041]

[0042] A preparation method of a super-tough photo-thermal energy storage three-dimensional network polymer, comprising the following steps:

[0043] 1) Under the protection of high-purity nitrogen, 40.0 - 100.0 g of flexible long-chain diols with different molecular weights (molecular weight of 4000 - 10000) are dried in a vacuum oven for 2 - 12 hours, and then 2.50 - 8.90 g of diisocyanate is added and dissolved in a three-necked flask equipped with an organic solvent. The molar ratio of the flexible long-chain diol to the diisocyanate is controlled to be 1:2. Under the condition of uniform stirring, when the temperature is 40 - 100 °C, heating and reflux reaction are carried out for 3 - 12 hours to obtain an -NCO-terminated prepolymer.

[0044] 2) Then, 1.38 g of p-benzoquinone dioxime is added to 20 - 50 ml of organic solvent and stirred until dissolved to obtain a p-benzoquinone dioxime organic solution. The above solution is dropped into the prepolymer obtained in 1), and the molar ratio of the flexible long-chain diol to p-benzoquinone dioxime is controlled to be 1:1. Under the protection of high-purity nitrogen, heating and reflux stirring reaction are carried out at a temperature of 40 - 120 °C for 2 - 6 hours.

[0045] 3) 1.49 - 2.98 g of triethanolamine is added to 20 - 50 ml of organic solvent and stirred until dissolved to obtain a triethanolamine organic solution, and then the obtained solution is added to 2). The molar ratio of the flexible long-chain diol to triethanolamine is controlled to be 1:1 - 2, and after stirring for 10 - 30 minutes, a uniform dark brown liquid is obtained.

[0046] The liquid obtained in step 3) is poured into a polytetrafluoroethylene mold, placed in a vacuum oven at 30 - 50 °C and heated for 2 - 4 hours, and then the temperature is raised to 60 - 120 °C for curing treatment for 2 - 4 hours to obtain a super-tough photo-thermal energy storage polymer material.

[0047] Furthermore, the flexible long-chain diol is polyethylene glycol (PEG), polybutylene glycol (PTMG), or a mixture of both.

[0048] Further, the organic solvent is N,N-dimethylformamide, tetrahydrofuran, N,N-dimethylacetamide, dimethyl sulfoxide, etc.

[0049] Further, the diisocyanate is toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), etc.

[0050] Example 1

[0051] Under the protection of high-purity nitrogen, 60.0 g of polyethylene glycol with a molecular weight of 6000 (PEG6000, 0.01 mol) was dried in a vacuum oven at 110 °C for 2 hours, and then 4.44 g of isophorone diisocyanate (0.02 mol) was added and dissolved in a three-necked flask containing ultra-dry tetrahydrofuran solvent. The molar ratio of PEG6000 to diisocyanate was controlled to be 1:2. Under the condition of uniform stirring, when the temperature was 50 °C, heating and reflux reaction were carried out for 2 hours to obtain an -NCO-terminated prepolymer. Then, 1.38 g of p-benzoquinone dioxime was added to 20 ml of tetrahydrofuran solvent and stirred to dissolve to obtain a p-benzoquinone dioxime organic solution. The above solution was dropped into the -NCO-terminated prepolymer, and the molar ratio of PEG6000 to p-benzoquinone dioxime was controlled to be 1:1. Under the protection of high-purity nitrogen, heating and reflux stirring reaction were carried out at 40 °C for 6 hours.

[0052] 1.49 g of triethanolamine was added to 20 ml of tetrahydrofuran solvent and stirred to dissolve to obtain a triethanolamine tetrahydrofuran solvent solution. Then, the obtained solution was added to the above solution, and the molar ratio of flexible long-chain diol to triethanolamine was controlled to be 1:1. After stirring for 10 minutes, a uniform black-brown liquid was obtained. Then, the obtained liquid was poured into a polytetrafluoroethylene mold and placed in a vacuum oven at 30 °C for heating for 2 hours, and then the temperature was raised to 60 °C for curing treatment for 2 hours to obtain a super-tough photothermal energy storage polymer material. This super-tough photothermal energy storage polymer material was named Y1, and its molecular structure is as follows:

[0053]

[0054] The specific reaction equation for its synthesis is as Figure 1 shown, and the Y1 sample is as Figure 2 shown. The chemical structure characteristic peaks of the Y1 sample were tested by Fourier infrared, and its curve is as Figure 3 , and through Figure 3 it can be seen that the synthesis of Y1 was successful. And the crystallization performance of Y1 was tested by X-ray diffraction, as Figure 4It can be seen that Y1 has good crystallization ability. A differential scanning calorimeter (DSC) was used to test the endothermic and exothermic conditions of Y1 under heating and cooling. The test conditions used in this invention are as follows: After heating at 40 K / min in the early stage to eliminate the thermal history, then cooling and heating cycles were carried out at 10 K / min. From Figure 5 it can be seen that Y1 has endothermic and exothermic peaks, indicating that it has the ability to absorb and release heat of the phase change material. The mechanical properties of Y were tested, such as Figure 6 it can be seen that the elongation at break of the sample reached 900%. Then, the temperature change curve of the sample was tested by irradiating with a near-infrared lamp and heating on a 70 °C hot stage in sequence, such as Figure 7 and Figure 8 , it can be seen that the sample has the abilities of light absorption, heat storage and photothermal conversion.

[0055] Example 2

[0056] Under the protection of high-purity nitrogen, 40.0 g of polyethylene glycol with a molecular weight of 4000 (PEG4000, 0.01 mol) was dried in a vacuum oven at 120 °C for 4 hours, and then 3.36 g of hexamethylene diisocyanate (0.02 mol) was added and dissolved in a three-necked flask containing ultra-dry tetrahydrofuran solvent, and the molar ratio of PEG4000 to diisocyanate was controlled to be 1:2. Under the condition of uniform stirring, when the temperature was 60 °C, heating reflux reaction was carried out for 6 hours to obtain an -NCO-terminated prepolymer. Then, 1.38 g of p-benzoquinone dioxime was added to 50 ml of tetrahydrofuran solvent and stirred to dissolve to obtain a p-benzoquinone dioxime organic solution, and the above solution was added dropwise to the -NCO-terminated prepolymer, and the molar ratio of PEG4000 to p-benzoquinone dioxime was controlled to be 1:1. Under the protection of high-purity nitrogen, heating and reflux stirring reaction were carried out at 50 °C for 5 hours.

[0057] 1.98 g of triethanolamine was added to 30 ml of tetrahydrofuran solvent and stirred to dissolve to obtain a triethanolamine tetrahydrofuran solvent solution. The molar ratio of the flexible long-chain diol to triethanolamine was controlled to be 1:1.3, and then the obtained solution was added to the above solution. After stirring for 30 minutes, a uniform dark brown liquid was obtained. Then, the obtained liquid was poured into a polytetrafluoroethylene mold and placed in a vacuum oven at 40 °C for heating for 2 hours, and then the temperature was raised to 70 °C for curing treatment for 1 hour to obtain a super-tough photothermal energy storage polymer material. This super-tough photothermal energy storage polymer material is named Y2, and its molecular structure is as follows:

[0058]

[0059] Example 3

[0060] Under the protection of high-purity nitrogen, 80.0 g of polyethylene glycol with a molecular weight of 8000 (PEG8000, 0.01 mol) was dried in a vacuum oven at 100 °C for 4 hours, and then 3.48 g of toluene diisocyanate (0.02 mol) was added and dissolved in a three-necked flask containing ultra-dry N,N-dimethylformamide solvent. The molar ratio of PEG8000 to diisocyanate was controlled to be 1:2. Under the condition of uniform stirring, when the temperature was 80 °C, heating reflux reaction was carried out for 4 hours to obtain an -NCO-terminated prepolymer. Then, 1.38 g of p-benzoquinone dioxime was added to 50 ml of N,N-dimethylformamide solvent and stirred to dissolve to obtain a p-benzoquinone dioxime organic solution. The above solution was dropped into the -NCO-terminated prepolymer, and the molar ratio of PEG8000 to p-benzoquinone dioxime was controlled to be 1:1. Under the protection of high-purity nitrogen, heating and reflux stirring reaction were carried out at 100 °C for 4 hours.

[0061] 2.98 g of triethanolamine was added to 30 ml of N,N-dimethylformamide solvent and stirred to dissolve to obtain a triethanolamine solution. The molar ratio of flexible long-chain diol to triethanolamine was controlled to be 1:2, and then the obtained solution was added to the above solution. After stirring for 10 minutes, a uniform dark brown liquid was obtained. Then, the obtained liquid was poured into a polytetrafluoroethylene mold and placed in a vacuum oven at 50 °C for heating for 2 hours, and then the temperature was raised to 100 °C for curing treatment for 1 hour to obtain a super-tough photothermal energy storage polymer material. This super-tough photothermal energy storage polymer material was named Y3, and its molecular structure is as follows:

[0062]

[0063] Example 4

[0064] Under the protection of high-purity nitrogen, 100.0 g of poly(tetramethylene glycol) with a molecular weight of 10000 (PTMG10000, 0.01 mol) was dried in a vacuum oven at 100 °C for 12 hours, and then 5.00 g of diphenylmethane diisocyanate (0.02 mol) was added and dissolved in a three-necked flask containing ultra-dry N,N-dimethylacetamide solvent. The molar ratio of PTMG10000 to diisocyanate was controlled to be 1:2. Under the condition of uniform stirring, when the temperature was 100 °C, heating reflux reaction was carried out for 12 hours to obtain an -NCO-terminated prepolymer. Then, 1.38 g of p-benzoquinone dioxime was added to 50 ml of N,N-dimethylacetamide solvent and stirred to dissolve to obtain a p-benzoquinone dioxime organic solution. The above solution was dropped into the -NCO-terminated prepolymer, and the molar ratio of PTMG10000 to p-benzoquinone dioxime was controlled to be 1:1. Under the protection of high-purity nitrogen, heating and reflux stirring reaction were carried out at 120 °C for 2 hours.

[0065] 2.24 g of triethanolamine was added to 30 ml of N,N-dimethylacetamide solvent and stirred until dissolved to obtain a triethanolamine solution. The molar ratio of the flexible long-chain diol to triethanolamine was controlled to be 1:1.5, and then the resulting solution was added to the above solution. After stirring for 30 minutes, a uniform dark brown liquid was obtained. Then the obtained liquid was poured into a polytetrafluoroethylene mold and placed in a vacuum oven at 50 °C for 4 hours of heating, and then the temperature was raised to 120 °C for 4 hours of curing treatment to obtain a super-tough photothermal energy storage polymer material. This super-tough photothermal energy storage polymer material was named Y4, and its molecular structure is as follows:

[0066]

[0067] Example 5

[0068] Under the protection of high-purity nitrogen, 100.0 g of polybutylene glycol with a molecular weight of 10,000 and polyethylene glycol (PTMG10000, PEG1000, with a ratio of 1:1, 0.01 mol) was dried in a vacuum oven at 100 °C for 12 hours, and then 5.25 g of dicyclohexylmethane diisocyanate (0.02 mol) was added and dissolved in a three-necked flask equipped with ultra-dry dimethyl sulfoxide solvent. The molar ratio of PTMG10000 to diisocyanate was controlled to be 1:2. Under the condition of uniform stirring and at a temperature of 100 °C, heating and reflux reaction were carried out for 10 hours to obtain an -NCO-terminated prepolymer. Then 1.38 g of p-benzoquinone dioxime was added to 40 ml of tetrahydrofuran and stirred until dissolved to obtain a p-benzoquinone dioxime organic solution. The above solution was dropped into the -NCO-terminated prepolymer, and the molar ratio of the long-chain diol to p-benzoquinone dioxime was controlled to be 1:1. Under the protection of high-purity nitrogen, heating and reflux stirring reaction were carried out at a temperature of 120 °C for 2 hours.

[0069] 2.53 g of triethanolamine was added to 30 ml of tetrahydrofuran solvent and stirred until dissolved to obtain a triethanolamine solution. The molar ratio of the flexible long-chain diol to triethanolamine was controlled to be 1:1.7, and then the resulting solution was added to the above solution. After stirring for 20 minutes, a uniform dark brown liquid was obtained. Then the obtained liquid was poured into a polytetrafluoroethylene mold and placed in a vacuum oven at 50 °C for 4 hours of heating, and then the temperature was raised to 120 °C for 4 hours of curing treatment to obtain a super-tough photothermal energy storage polymer material. This super-tough photothermal energy storage polymer material was named Y5, and its molecular structure is as follows:

[0070]

[0071] In the present invention, photothermal function and phase change functional groups are block-copolymerized onto the molecular chain through covalent bonds, and a three-dimensional network structure is formed through the curing and cross-linking of trihydric alcohols, avoiding the interface problems of composite materials, realizing the dual functions of photothermal energy storage and super toughness, and ensuring the wear resistance, wash resistance, fatigue resistance and other properties of the polymer material.

[0072] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A super-tough photothermal energy storage three-dimensional network polymer, characterized in that, First, an isocyanate group-terminated prepolymer is prepared by reacting a diisocyanate with a flexible long-chain diol. Then, the prepolymer is reacted with a dioxime-based monomer to prepare a linear oligomer polymer with a photothermal conversion function and a phase change group block. Finally, the linear oligomer polymer is cured with a trifunctional triol to form a three-dimensional network polymer, and its molecular structure is ； A method for preparing a super-tough photothermal energy storage three-dimensional network polymer, comprising the following steps: S1. Under the protection of high-purity nitrogen, the flexible long-chain diol is vacuum-dried for 2 to 12 h and then added to the diisocyanate, and the reaction is carried out under the condition of uniform stirring to obtain an -NCO-terminated prepolymer; S2. p-Benzoquinone dioxime is added to an organic solvent and stirred to dissolve to obtain a p-benzoquinone dioxime organic solution. Then, the p-benzoquinone dioxime organic solution is added dropwise to the -NCO-terminated prepolymer and heated and refluxed with stirring to obtain a linear oligomer polymer with a photothermal conversion function and a phase change group block; S3. Triethanolamine is added to an organic solvent and stirred to dissolve to obtain a triethanolamine organic solution. Then, the triethanolamine organic solution is added to the linear oligomer polymer, and after stirring, a uniform dark brown liquid is obtained; S4. The uniform dark brown liquid is poured into a polytetrafluoroethylene mold and placed in a vacuum oven at 30 to 50 °C and heated for 2 to 4 hours, and then the temperature is raised to 60 to 120 °C for curing treatment for 2 to 4 h to obtain a super-tough photothermal energy storage three-dimensional network polymer; The molar ratio of the flexible long-chain diol to the diisocyanate is 1:2; the molar ratio of the flexible long-chain diol to p-benzoquinone dioxime is 1:1; The diisocyanate is isophorone diisocyanate IPDI; The flexible long-chain diol is polyethylene glycol PEG.

2. The super-tough photo-thermal energy storage three-dimensional network polymer according to claim 1, wherein: The molecular weight of the flexible long-chain diol is 4000 to 10000.

3. The super-tough photothermal energy storage three-dimensional network polymer according to claim 1, characterized in that: In step S1, the reaction under the condition of uniform stirring is specifically: reflux reaction at 40 to 100 °C for 3 to 12 h.

4. The super-tough photothermal energy storage three-dimensional network polymer according to claim 1, wherein: In step S2, the heating and reflux stirring reaction is specifically: under the protection of high-purity nitrogen, reflux stirring reaction at a temperature of 40 to 120 °C for 2 to 6 h.

5. The super-tough photo-thermal energy storage three-dimensional network polymer according to claim 1, wherein: In step S3, the molar ratio of the added triethanolamine to the flexible long-chain diol is 1 to 2:1, and the stirring time is 10 to 30 min.

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