Intrinsic self-repairing microcapsule prepared by thiol-ene click reaction and preparation method of intrinsic self-repairing microcapsule
The microcapsules prepared through the thiol-ene click reaction use dynamic disulfide bonds to achieve self-healing under heating conditions, solving the problem of difficult cracks to close under the curved microcapsules morphology and achieving adaptive repair effect.
Patent Information
- Application Number
- CN202510466046.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2025-07-29
AI Technical Summary
When existing polymer microcapsules are damaged in curved surface form, cracks are difficult to close, self-repairing effect is poor, and effective self-repairing is difficult to achieve effective self-repair.
Microcapsules were prepared by thiol-ene click reaction, and the shell was crosslinked by liquid thiol-terminated polysulfide oligomer and acrylate to form a shell, imparting the self-healing properties of the microcapsules and using dynamic disulfide bonds to achieve shape recovery under heating conditions.
Microcapsules can automatically close wounds under heating conditions to achieve adaptive repair, and control the number and density of disulfide bonds by regulating components to achieve controllability of structure and performance.
Smart Images
Figure CN120383732A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to intrinsically self - healing microcapsules, and in particular, to an intrinsically self - healing microcapsule prepared by a thiol - ene click reaction and a preparation method thereof. Background Art
[0002] Polymer microcapsules are core - shell structured particles with natural or synthetic polymer materials as the wall material and encapsulating functional core materials. Their unique three - dimensional confinement structure can isolate the core material from the external environment, effectively protecting the physical and chemical stability of the core material, and showing important application values in fields such as phase - change energy storage, drug sustained - release, and self - healing materials. However, during the application process of microcapsules, they will inevitably be damaged physically or chemically to varying degrees, thus affecting the physical and chemical properties of the core material. Endowing polymer microcapsule materials with intrinsic self - healing properties is an effective way to extend their service life. However, there are few reports on intrinsically self - healing microcapsules at present, which is mainly related to the shape and structure of microcapsules. Microcapsules have various shapes and are spherical because the core material they encapsulate is mostly liquid in most cases. This spherical shape is a curved surface structure, and the curved surface has radial loads and a certain curvature. When damaged by external forces, cracks appear in the microcapsule shell and the microcapsule deforms due to the external shear force. Different from planar cracks, this deformation makes the curved surface cracks unable to close, bringing great challenges to the self - healing of microcapsules themselves. Therefore, it is difficult to achieve the self - healing of polymer microcapsules only by molecular chain diffusion, and the synergistic problem of curved surface morphology recovery and molecular repair must be solved simultaneously. Summary of the Invention
[0003] Aiming at the above - mentioned defects of the prior art, the present invention provides an intrinsically self - healing microcapsule prepared by a thiol - ene click reaction, and the prepared intrinsically self - healing microcapsule can complete the repair of damage under heating conditions.
[0004] The technical object of the present invention is achieved by the following technical solutions:
[0005] In the first aspect of the present invention, there is provided an intrinsically self - healing microcapsule prepared by a thiol - ene click reaction. The microcapsule is composed of an external shell layer and a core material encapsulated inside the shell layer. The shell layer is cross - linked by a thiol - ene click reaction of a liquid thiol - terminated polysulfide oligomer and an acrylate.
[0006] The microcapsules of the present invention encapsulate the core material by initiating a thiol-ene click reaction between the thiol groups in the liquid thiol-terminated polysulfide oligomer and the alkenyl groups of the acrylate, thereby forming microcapsules. Moreover, due to the presence of dynamic disulfide bonds in the molecular structure of the liquid thiol-terminated polysulfide oligomer, the microcapsules are endowed with self-healing properties, that is, the external self-healing material is endowed with multiple healing properties. The damaged and deformed microcapsules rely on their shape memory properties and can restore their original curved shape under heating conditions, enabling the wound to close autonomously and achieving adaptive repair.
[0007] Preferably, the mass ratio of the liquid thiol-terminated polysulfide oligomer to the acrylate is 40-100:10-50; further, it can be 60-80:20-30.
[0008] Preferably, the acrylate is selected from one or more of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, cyclohexanedimethanol-1,4-diacrylate, tricyclodecane dimethanol diacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipropylene glycol diacrylate, 1,10-decanediol dimethacrylate.
[0009] Preferably, the liquid thiol-terminated polysulfide oligomer is a mixture of one or two of LP-33, LP-55, LP-56, LP-32, LP-23, LP-2, LP-31.
[0010] Preferably, the core material is a mixture of one or two of n-tetradecane, n-octadecane, n-heptadecane, n-eicosane.
[0011] On the other hand, the present invention also provides a preparation method of the intrinsic self-healing microcapsules, comprising the following steps:
[0012] 1) Mix the surfactant and deionized water under stirring at room temperature,
[0013] 2) Add the photoinitiator to the reaction system obtained in step 1) and stir to mix,
[0014] 3) Add the liquid thiol-terminated polysulfide oligomer, acrylate, and core material to the reaction system obtained in step 2) for reaction,
[0015] 4) Irradiate the reaction system obtained in step 3) with ultraviolet light while stirring,
[0016] 5) Finally, filter, wash repeatedly with deionized water, and air dry at room temperature to obtain the microcapsules.
[0017] First, a surfactant and a photoinitiator are separately dispersed in deionized water, and then a liquid thiol-terminated polysulfide oligomer, an acrylate, and a core material are added. Further, under the action of ultraviolet light, a thiol-ene click reaction between the thiol groups in the liquid thiol-terminated polysulfide oligomer and the thiol groups of the acrylate can be initiated, thereby coating the core material to form microcapsules. The preparation process is simple and the conditions are easy to control.
[0018] Preferably, based on parts by weight, the amounts of each raw material are as follows: 10 - 50 parts of acrylate, 40 - 100 parts of liquid thiol-terminated polysulfide oligomer, 50 - 70 parts of surfactant, 10 - 40 parts of core material, 1 - 10 parts of photoinitiator, and the weight ratio of the surfactant to deionized water is 50 - 70:600.
[0019] Preferably, the surfactant is one or a mixture of two of sodium dodecyl sulfate, gum arabic, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, and sodium alginate.
[0020] Preferably, the photoinitiator is one or a mixture of two of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.
[0021] Preferably, in step 1), the stirring and mixing time is 0.5 - 3 h, in step 2), the stirring and mixing time is 0.5 - 2 h, in step 3), the reaction time is 0.5 - 1 h; in step 4), the ultraviolet light irradiation time is 0.5 - 2 h.
[0022] Preferably, in step 5), the number of times of washing with deionized water is 2 - 5 times.
[0023] The beneficial effects of the present invention are as follows:
[0024] 1. The intrinsic self-healing microcapsules of the present invention can restore the shape before damage under heating conditions, enabling the wound to close autonomously, which is beneficial for the self-adaptive repair of the injury.
[0025] 2. The intrinsic self-healing microcapsules of the present invention can complete self-healing of the damage under mild conditions through the action of disulfide bonds, and the number and density of disulfide bonds can be controlled by regulating the components, realizing the controllability of structure and performance.
[0026] 3. The raw materials used in the microcapsules of the present invention are already industrial products in large-scale production, which are cheap and easily available. The synthesis process does not require special conditions and equipment, the synthesis process is easy to control, the process is simple, and the cost is low. Description of the Drawings
[0027] Figure 1 Scanning electron microscope photograph of the morphology of the intrinsic self-healing microcapsules prepared in Example 1;
[0028] Figure 2 Scanning electron microscope photograph of the cut intrinsic self-healing microcapsules prepared in Example 1;
[0029] Figure 3 Scanning electron microscope photograph of the repair state of the surface scratch deformation of the intrinsic self-healing microcapsules prepared in Example 1;
[0030] Figure 4 Scanning electron microscope photograph of the completely repaired state of the surface scratch of the intrinsic self-healing microcapsules prepared in Example 1. Detailed implementation mode
[0031] The present invention prepares an intrinsic self-healing microcapsule through a thiol-ene click reaction. The microcapsule is composed of an outer shell layer and a core material coated inside the shell layer. The shell layer is crosslinked by a thiol-ene click reaction of a liquid thiol-terminated polysulfide oligomer and an acrylate.
[0032] By using a liquid thiol-terminated polysulfide oligomer, dynamic covalent bonds, hard segments (crystalline / vitrified microdomains) and soft segments (amorphous chain segments) are efficiently introduced into the microcapsule structure to endow it with self-healing performance and shape memory performance. When the microcapsule is damaged, temperature stimulation triggers shape recovery to close the crack; the dynamic disulfide bonds in the soft segment achieve interfacial molecular reconstruction through bond exchange reactions to complete the repair of the microcapsule and extend its service life. Specifically, the deformed microcapsule after damage relies on its shape memory performance and can recover its original curved shape under heating conditions to autonomously close the wound and achieve self-adaptive repair. For example, repair can be achieved at 80-150 °C by heating for 10-30 h.
[0033] Furthermore, the number and density of disulfide bonds can be controlled by regulating the components to achieve controllable structure and performance. Preferably, the mass ratio of the liquid thiol-terminated polysulfide oligomer to the acrylate is 40-100:10-50, and the obtained microcapsules have good mechanical strength and self-healing performance.
[0034] The acrylate synthesized by the microcapsules of the present invention is selected from one or more of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, cyclohexanedimethanol-1,4-diacrylate, tricyclodecane dimethanol diacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipropylene glycol diacrylate, 1,10-decanediol dimethacrylate.
[0035] The liquid mercapto-terminated polysulfide oligomers for synthesizing the microcapsules of the present invention are one or a mixture of two of LP-33, LP-55, LP-56, LP-32, LP-23, LP-2, and LP-31.
[0036] The core material of the microcapsules of the present invention can be one or a mixture of two of n-tetradecane, n-octadecane, n-heptadecane, and n-eicosane.
[0037] In a preferred embodiment, the microcapsules of the present invention can be prepared by the following method:
[0038] 1) Mix the surfactant and deionized water under stirring at room temperature.
[0039] 2) Add the photoinitiator to the reaction system obtained in step 1) and stir to mix.
[0040] 3) Add the liquid mercapto-terminated polysulfide oligomer, acrylate, and core material to the reaction system obtained in step 2) and react.
[0041] 4) Irradiate the reaction system obtained in step 3) with ultraviolet light while stirring.
[0042] 5) Finally, filter, wash repeatedly with deionized water, and air-dry at room temperature to obtain the microcapsules.
[0043] First, the surfactant and the photoinitiator are separately dispersed in deionized water to form a continuous aqueous phase, and then the oil phases such as the liquid mercapto-terminated polysulfide oligomer, acrylate, and core material are added. Further, under the action of ultraviolet light, a thiol-ene click reaction between the mercapto groups in the liquid mercapto-terminated polysulfide oligomer and the mercapto groups of the acrylate can be initiated at the water-oil phase interface, thereby coating the core material to form microcapsules. The preparation process is simple and the conditions are easy to control.
[0044] The surfactant described above can be one or a mixture of two of sodium dodecyl sulfate, gum arabic, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, and sodium alginate.
[0045] The photoinitiator described above can be one or a mixture of two of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.
[0046] In a preferred embodiment, the amounts of each raw material are as follows in parts by weight: 10 - 50 parts of acrylate, 40 - 100 parts of liquid thiol-terminated polysulfide oligomer, 50 - 70 parts of surfactant, 10 - 40 parts of core material, 1 - 10 parts of photoinitiator, and the weight ratio of surfactant to deionized water is 50 - 70:600.
[0047] In a preferred embodiment, the stirring and mixing time in step 1) is 0.5 - 3 h, the stirring and mixing time in step 2) is 0.5 - 2 h, the reaction time in step 3) is 0.5 - 1 h; the ultraviolet light irradiation time in step 4) is 0.5 - 2 h.
[0048] In a preferred embodiment, the number of times of washing with deionized water in step 5) is 2 - 5 times.
[0049] The preferred embodiments of the present invention will be described in detail below in conjunction with examples. It should be understood that the following examples are given only for the purpose of illustration and are not used to limit the scope of the present invention. Those skilled in the art can make various modifications and substitutions to the present invention without departing from the purpose and spirit of the present invention.
[0050] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial channels or prepared by conventional methods in the art. The liquid thiol-terminated polysulfide oligomer therein is purchased from Thiokol Co., Ltd.
[0051] The unit of parts by weight mentioned in the examples is gram.
[0052] Example 1
[0053] 1. Preparation of Intrinsic Self-Healing Microcapsules
[0054] 50 parts of gum arabic and 600 parts of deionized water were reacted for 0.5 hour under stirring at room temperature, 1 part of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone was added to the reaction system and stirred for 0.5 hour, then 60 parts of LP-33, 20 parts of polyethylene glycol diacrylate, and 10 parts of n-tetradecane were added and reacted for another 0.5 hour, and then irradiated with an ultraviolet lamp for 1 hour while stirring. Finally, it was filtered, washed repeatedly with deionized water 3 times, and air-dried at room temperature for 48 hours to obtain intrinsic self-healing microcapsules.
[0055] 2. Self-Healing Performance Test of Intrinsic Self-Healing Microcapsules
[0056] The product obtained was observed by scanning electron microscope, and it was found that the intrinsic self-healing microcapsules prepared in Example 1 were uniformly distributed spheres, asFigure 1 As shown. Cut the intrinsic self-healing microcapsules with a blade, and it can be seen that the microcapsules are deformed under shear force ( Figure 2 ). Place the damaged microcapsules in an oven at 100 °C and heat for 10 hours. Observe the morphology of the microcapsules using a scanning electron microscope, and the deformed microcapsules can all recover their original curved shape ( Figure 3 ). Further extend the heating time to 24 hours, and all the damaged microcapsules can be completely repaired ( Figure 4 ).
[0057] Example 2
[0058] 1. Preparation of Intrinsic Self-Healing Microcapsules
[0059] React 70 parts of gum arabic and 600 parts of deionized water under stirring at room temperature for 3 hours. Add 2 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one to the reaction system and stir for 2 hours. Then add 80 parts of LP-55, 20 parts of cyclohexanedimethanol-1,4-diacrylate, and 20 parts of n-tetradecane and continue to react for 1 hour. Then irradiate with an ultraviolet lamp for 0.5 hour while stirring. Finally, filter, wash repeatedly with deionized water 5 times, and air-dry at room temperature for 24 hours to obtain the intrinsic self-healing microcapsules.
[0060] 2. Self-Healing Performance Test of Intrinsic Self-Healing Microcapsules
[0061] Observe the obtained product using a scanning electron microscope, and it is found that the intrinsic self-healing microcapsules prepared in Example 2 are uniformly distributed spheres. Cut the intrinsic self-healing microcapsules with a blade, and it can be seen that the microcapsules are deformed under shear force. Place the damaged microcapsules in an oven at 100 °C and heat for 10 hours, and the deformed microcapsules can all recover their original curved shape. Further extend the heating time to 24 hours, and all the damaged microcapsules can be completely repaired.
[0062] Example 3
[0063] 1. Preparation of Intrinsic Self-Healing Microcapsules
[0064] React 50 parts of sodium dodecyl sulfate and 600 parts of deionized water under stirring at room temperature for 2 hours. Add 5 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one to the reaction system and stir for 2 hours. Then add 70 parts of LP-23, 30 parts of tricyclodecane dimethanol diacrylate, and 30 parts of n-eicosane and continue to react for 1 hour. Then irradiate with an ultraviolet lamp for 2 hours while stirring. Finally, filter, wash repeatedly with deionized water 4 times, and air-dry at room temperature for 24 hours to obtain the intrinsic self-healing microcapsules.
[0065] 2. Self-Healing Performance Test of Intrinsic Self-Healing Microcapsules
[0066] The product observed by scanning electron microscope shows that the intrinsically self-healing microcapsules prepared in Example 3 are uniformly distributed spheres. When the intrinsically self-healing microcapsules are cut with a blade, it can be seen that the microcapsules are deformed under shear force. The damaged microcapsules are placed in an oven at 100 °C for 10 hours, and the deformed microcapsules can all recover their original curved surface shape. Further extending the heating time to 24 hours, the damaged microcapsules can all be completely repaired.
[0067] Example 4
[0068] 1. Preparation of intrinsically self-healing microcapsules
[0069] 60 parts of gum arabic and 600 parts of deionized water are reacted for 1 hour under stirring at room temperature. 1 part of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is added to the reaction system and stirred for 1 hour. Then 70 parts of LP-33, 30 parts of pentaerythritol triacrylate, and 30 parts of n-tetradecane are added and the reaction continues for 1 hour. Then it is irradiated with an ultraviolet lamp for 1 hour while stirring. Finally, it is filtered, washed repeatedly with deionized water 3 times, and air-dried at room temperature for 24 hours to obtain the intrinsically self-healing microcapsules.
[0070] 2. Self-healing performance test of intrinsically self-healing microcapsules
[0071] The product observed by scanning electron microscope shows that the intrinsically self-healing microcapsules prepared in Example 4 are uniformly distributed spheres. When the intrinsically self-healing microcapsules are cut with a blade, it can be seen that the microcapsules are deformed under shear force. The damaged microcapsules are placed in an oven at 100 °C for 10 hours, and the deformed microcapsules can all recover their original curved surface shape. Further extending the heating time to 24 hours, the damaged microcapsules can all be completely repaired.
[0072] Comparative Example 1
[0073] 1. Preparation of microcapsules
[0074] 50 parts of gum arabic and 600 parts of deionized water are reacted for 1 hour under stirring at room temperature. 1 part of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is added to the reaction system and stirred for 1 hour. Then 40 parts of LP-33, 5 parts of pentaerythritol triacrylate, and 30 parts of n-tetradecane are added and the reaction continues for 1 hour. Then it is irradiated with an ultraviolet lamp for 0.5 hour while stirring. Finally, it is filtered, washed repeatedly with deionized water 3 times, and air-dried at room temperature for 24 hours to obtain the intrinsically self-healing microcapsules.
[0075] 2. Self-healing performance test of microcapsules
[0076] The products observed by scanning electron microscopy showed that many microcapsule shell layers were broken. When the unbroken microcapsules were cut with a blade, microcapsule breakage occurred. In addition, even for the unbroken microcapsules, after being heated in an oven at 100 °C for 10 hours, the deformed microcapsules could not fully recover their original curved surface shape. Further extending the heating time to 24 hours, the damaged microcapsules were not fully repaired either.
[0077] This may be due to insufficient cross-linking of acrylate, resulting in a decrease in mechanical strength and thus breakage. Moreover, insufficient cross-linking of acrylate will also lead to too low a density of disulfide bonds, resulting in a significant reduction in self-healing efficiency. Therefore, the phenomenon that the cracks were not completely closed after heating occurred.
[0078] Comparative Example 2
[0079] 1. Preparation of microcapsules
[0080] 60 parts of gum arabic and 600 parts of deionized water were reacted under stirring at room temperature for 1 hour. 5 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one were added to the reaction system and stirred for 1 hour. Then 30 parts of LP-55, 40 parts of tricyclodecane dimethanol diacrylate, and 20 parts of n-octadecane were added and the reaction continued for 1 hour. Then it was irradiated with an ultraviolet lamp for 1 hour while stirring. Finally, it was filtered, washed repeatedly with deionized water 3 times, and air-dried at room temperature for 48 hours to obtain the intrinsically self-healing microcapsules.
[0081] 2. Self-healing performance test of microcapsules
[0082] The products observed by scanning electron microscopy showed that some microcapsule shell layers were broken. When the unbroken microcapsules were cut with a blade, microcapsule breakage occurred. In addition, even for the unbroken microcapsules, after being heated in an oven at 100 °C for 10 hours, most of the microcapsules could not fully recover their original curved surface shape. Further extending the heating time to 24 hours, the damaged microcapsules were not fully repaired either.
[0083] This may be because the self-healing activity is reduced due to insufficient number of disulfide bonds in the shell layer, resulting in only partial closure of the cracks or inability to restore the original curved surface shape after heating. In addition, due to insufficient disulfide bonds, the microcapsules may be brittle due to insufficient cross-linking density and are easily fragmented under mechanical stress. Therefore, some of the prepared microcapsules were broken.
[0084] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered to be within the scope described in this specification. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of this invention patent shall be subject to the appended claims.
Claims
1. An intrinsically self-healing microcapsule prepared by thiol-ene click reaction, characterized in that, The microcapsules are composed of an outer shell layer and a core material encapsulated inside the shell layer. The shell layer is crosslinked by a thiol-ene click reaction of a liquid thiol-terminated polysulfide oligomer and an acrylate.
2. The intrinsic self-healing microcapsule according to claim 1, wherein The acrylate selected from one or more of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, cyclohexanedimethanol-1,4-diacrylate, tricyclodecane dimethanol diacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipropylene glycol diacrylate, 1,10-decanediol dimethacrylate.
3. The intrinsic self-healing microcapsule according to claim 1, wherein The liquid thiol-terminated polysulfide oligomer is a mixture of one or two of LP-33, LP-55, LP-56, LP-32, LP-23, LP-2, LP-31.
4. The intrinsic self-healing microcapsule according to claim 1, characterized in that, The core material is a mixture of one or two of n-tetradecane, n-octadecane, n-heptadecane, n-eicosane.
5. The preparation method of the intrinsic self-healing microcapsules according to any one of claims 1-4, characterized in that, Including the following steps: 1) Mix the surfactant and deionized water under stirring at room temperature. 2) Add the photoinitiator to the reaction system obtained in step 1) and stir to mix. 3) Add the liquid thiol-terminated polysulfide oligomer, acrylate, and core material to the reaction system obtained in step 2) for reaction. 4) Irradiate the reaction system obtained in step 3) with ultraviolet light while stirring. 5) Finally, filter, wash repeatedly with deionized water, and air-dry at room temperature to obtain the microcapsules.
6. The preparation method according to claim 5, characterized in that, Based on parts by weight, the amounts of each raw material are as follows: acrylate 10 - 50 parts, liquid thiol-terminated polysulfide oligomer 40 - 100 parts, surfactant 50 - 70 parts, core material 10 - 40 parts, photoinitiator 1 - 10 parts, and the weight ratio of the surfactant to deionized water is 50 - 70:
600.
7. The preparation method according to claim 5, wherein The surfactant is a mixture of one or two of sodium dodecyl sulfate, gum arabic, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium alginate.
8. The preparation method according to claim 5, characterized in that, The photoinitiator is a mixture of one or two of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.
9. The preparation method according to claim 5, characterized in that, In step 1), the stirring and mixing time is 0.5 - 3 h, in step 2), the stirring and mixing time is 0.5 - 2 h, in step 3), the reaction time is 0.5 - 1 h; in step 4), the ultraviolet light irradiation time is 0.5 - 2 h.
10. The preparation method according to claim 5, characterized in that, In step 5), the number of times of washing with deionized water is 2 - 5 times.