CN113897011A - Impact-resistant flexible protective material and preparation method thereof - Google Patents
Impact-resistant flexible protective material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a protective material, in particular to an impact-resistant flexible protective material and a preparation method thereof, wherein the method comprises the following steps: s1: surface modification is carried out to improve high-performance fiber cloth; s2: cleaning and drying the obtained modified high-performance fiber cloth; s3: adding a reaction monomer, a cross-linking agent and an initiator into a solvent, and stirring until the reaction monomer, the cross-linking agent and the initiator are completely dissolved to obtain a hydrogel pre-polymerization solution; s4: arranging the modified high-performance fiber in a mold, injecting the obtained hydrogel pre-polymerization solution into the mold, standing until the hydrogel is completely soaked, and heating to initiate polymerization reaction; s5: and (5) soaking the composite material obtained in the step (S4) in a cleaning solution, replacing the solvent, and completely replacing to obtain the impact-resistant flexible protective material. Compared with the prior art, the invention realizes the preparation of the flexible composite material with impact resistance, bending and high energy consumption, and has the advantages of low surface density, easy preparation, stable performance, portability, easy wearing and the like compared with the existing material.
Description
Technical Field
The invention relates to a protective material, in particular to an impact-resistant flexible protective material and a preparation method thereof.
Background
The flexible protective material is a hotspot of research in the field of protection in recent years, and due to the diversification of modern combat modes and the improvement of individual protection consciousness and requirements, a comfortable and light flexible protective material with excellent protection capability is urgently needed. The traditional protective materials such as metal insertion plates, ceramic insertion plates, metal insertion plates compounded with high-performance fibers, thermosetting resin compounded with high-performance fibers and the like have higher density and poor bendability, and can not meet the requirement of flexible protection. In recent years, foamed plastics and shear thickening fluids have become the main subject of flexible protective materials due to their unique properties, and such materials are often combined with high performance fibers to achieve flexible protection. However, foamed plastics are generally thick in use due to their cushioning and protection mechanism based on a porous structure, which limits their application in personal protection. Shear thickening fluids are typically suspensions of dispersed phase particles and a media phase, which are not easily carried and worn in a normally liquid form; on the other hand, the suspension system has high requirement on stability in the using process, and the layering phenomenon may occur after long-term storage; in addition, when the suspension is compounded with the fiber, the problem that particles fall off the surface of the fiber can occur; all the above problems lead to the great reduction of the protective performance. The existing flexible anti-impact protective material mainly comprises a scaly steel plate embedded fiber cloth, a shear thickening fluid and a fiber cloth composite material.
The hydrogel is a very hydrophilic three-dimensional network structure gel, can be rapidly swelled in water and can keep a large volume of water in the swelled state without dissolving, and has the characteristics of stretchability, high toughness, high energy consumption and the like. Most of the hydrogels studied previously have good stretchability but low strength and modulus. Some high-strength high-modulus hydrogels are brittle and cannot meet strain requirements. Therefore, by designing the hydrogel network structure, the preparation of a stretchable hydrogel with high strength, high modulus and high toughness has certain challenges.
Chinese patent CN110746614A discloses a preparation method and application of an impact-resistant high-strength physical hydrogel, the structure of which is a three-dimensional network formed by mutual crosslinking of a polymerizable charged monomer and a neutral high-molecular polymer, and the preparation method is characterized in that the three-dimensional network structure contains metal ions. However, the patent does not disclose how the prepared hydrogel can be used in a flexible protective material; the performance is changed by adding metal ions to generate salting-out effect, and the method is easily influenced by the environment, so that the requirement on production equipment is high; low-temperature freezing is needed in the preparation process, so that the requirement on production equipment is further improved, and the production cost is increased.
Chinese patent CN103435951A discloses a nano-composite polymer double-network hydrogel and a preparation method thereof, the preparation steps are as follows: dissolving a first network monomer, a cross-linking agent and an initiator in the nano-particle-containing aqueous dispersion, pouring the obtained mixed solution into a mould, and heating and polymerizing to obtain the first network hydrogel. And dissolving the second network monomer, the cross-linking agent and the initiator in water, putting the first network hydrogel into the solution, swelling for 24 hours, and heating for polymerization to obtain the high-strength nano composite polymer double-network hydrogel. The compressive strength (10-30 MPa under 90% strain) of the double-network hydrogel is improved through nano reinforcement, the high tensile strength (0.1-0.6 MPa) can be kept, and the high tensile strength and the high modulus of the hydrogel material required by flexible protection are still different, so that the double-network hydrogel is not suitable for the protection field, especially the application in the military protection field.
Disclosure of Invention
The invention aims to solve at least one of the problems, and provides an anti-impact flexible protective material and a preparation method thereof, so that the preparation of an anti-impact, bendable and high-energy-consumption flexible composite material is realized, and compared with the existing material, the anti-impact flexible protective material has the advantages of low surface density, easiness in preparation, stable performance, portability, easiness in wearing and the like.
The purpose of the invention is realized by the following technical scheme:
the invention discloses a preparation method of an impact-resistant flexible protective material, which comprises the following steps:
s1: carrying out surface modification treatment on the high-performance fiber cloth to obtain modified high-performance fiber cloth;
s2: cleaning and drying the modified high-performance fiber cloth obtained in the step S1;
s3: adding a reaction monomer, a cross-linking agent and an initiator into a solvent, and stirring until the reaction monomer, the cross-linking agent and the initiator are completely dissolved to obtain a hydrogel pre-polymerization solution;
s4: arranging the modified high-performance fiber obtained in the step S2 in a mold, injecting the hydrogel pre-polymerization liquid obtained in the step S3 into the mold, standing until the modified high-performance fiber cloth is completely soaked, and heating to initiate polymerization reaction to obtain a hydrogel/fiber cloth composite material or an organogel/fiber cloth composite material;
s5: and (4) soaking the hydrogel/fiber cloth composite material or the organic gel/fiber cloth composite material obtained in the step (S4) in a cleaning solution, replacing the solvent, and completely replacing to obtain the impact-resistant flexible protective material.
Preferably, the high-performance fiber cloth in step S1 is an ultra-high molecular weight polyethylene fiber woven cloth, an ultra-high molecular weight polyethylene fiber unidirectional cloth, a kevlar fiber woven cloth, or a carbon fiber cloth.
Preferably, the surface modification treatment described in step S1 is a chemical treatment method, an ultraviolet irradiation grafting method, a plasma irradiation method, or a high-energy ray irradiation method. The surface hydrophilicity is obtained after the surface of the high-performance fiber cloth is modified, on one hand, the wettability of the hydrogel pre-polymerization liquid on the high-performance fiber cloth in the material preparation process can be improved, on the other hand, an interaction force can exist between the amide group on the surface of the high-performance fiber cloth and a hydrogel matrix, and the interface stability and the energy consumption performance are improved.
Preferably, the chemical reagent treatment method is to mix potassium dichromate, sulfuric acid and distilled water in proportion to prepare a chromic acid etching solution, and dispose the high-performance fiber in the chromic acid etching solution for treatment.
Preferably, the potassium dichromate, the sulfuric acid and the distilled water are mixed according to the proportion that the potassium dichromate, the sulfuric acid and the distilled water are mixed according to the mass ratio of 7:150: 12.
Preferably, the treatment time in the chromic acid etching solution is 1-2 min.
Preferably, the ultraviolet irradiation grafting method comprises the steps of soaking the high-performance fiber cloth in a photoinitiator solution for the first time, taking out the high-performance fiber cloth, irradiating the high-performance fiber cloth under ultraviolet light for the first time, immediately placing the high-performance fiber cloth in a mixed solution for the second time, soaking the high-performance fiber cloth in the mixed solution for the second time, taking out the high-performance fiber cloth, and irradiating the high-performance fiber cloth under ultraviolet light for the second time.
Preferably, the photoinitiator solution is obtained by mixing benzophenone, n-hexane and acetone, the concentration range of the benzophenone is 0.1-0.5 mol/L, and the volume ratio of the n-hexane to the acetone is 9: 1-1: 9. Preferably, the concentration of the benzophenone is 0.2mol/L, and the volume ratio of the n-hexane to the acetone is 7: 3.
Preferably, the soaking time of the primary soaking is 1-24 hours, and preferably 3 hours.
Preferably, the ultraviolet irradiation intensity of the primary irradiation is 1000W/h, and the front irradiation time and the back irradiation time of the high-performance fiber cloth are respectively 1-60 min. Preferably, the front and back irradiation time of the high-performance fiber cloth is 5min respectively.
Preferably, the mixed solution is an acetone/water mixed solution of acrylamide/N ', N' -methylene bisacrylamide, wherein the concentration of the acrylamide is 0.1-2 mol/L, the concentration of the N ', N' -methylene bisacrylamide is 0.01-0.2 mol/L, and the volume ratio of the acetone to the water is 2: 8-8: 2. Preferably, the acrylamide concentration is 0.2mol/L, the N ', N' -methylenebisacrylamide concentration is 0.02mol/L, and the volume ratio of acetone to water is 5: 5.
Preferably, the soaking time of the secondary soaking is 1-24 hours, and preferably 3 hours.
Preferably, the ultraviolet irradiation intensity of the secondary irradiation is 1000W/h, and the front irradiation time and the back irradiation time of the high-performance fiber cloth are respectively 1-60 min, preferably 2 min.
Preferably, the plasma irradiation method is to arrange the high-performance fiber in a 300W plasma oxygen atmosphere for irradiation, and then immediately soak the high-performance fiber in an aqueous solution of 2 wt% of silane coupling agent KH 570.
Preferably, the irradiation of the high-performance fiber cloth in the 300W plasma oxygen atmosphere is to irradiate the high-performance fiber cloth in the 300W plasma oxygen atmosphere on the front surface and the back surface for 5min respectively.
Preferably, the soaking time is 12 hours.
Preferably, the high-energy radiation method is gamma radiation method, the dose rate is about 92rad/s, and the total dose is 5-30 kGy.
Compared with a chemical reagent treatment method, the ultraviolet irradiation method has higher operation safety; compared with a plasma irradiation method, the modification effect is better; compared with a high-energy ray irradiation method, the steps are simpler and more convenient and are easy to realize; in addition, the damage of the ultraviolet irradiation method to the mechanical property of the fiber cloth is smaller than that of other fiber cloth, and the ultraviolet irradiation method is preferably adopted to carry out surface modification treatment on the high-performance fiber cloth.
Preferably, the cleaning and drying in step S2 is to sequentially soak and wash the high-performance fiber cloth with deionized water and ethanol, and then dry the high-performance fiber cloth in an oven at 60 ℃ for 1 to 24 hours, preferably 12 hours.
Preferably, the reaction monomer in step S3 is one or more of 1-vinylimidazole, methacrylic acid, acrylamide, chitosan, acrylic acid, sodium styrene sulfonate and methacryl propyl trimethyl ammonium chloride, and the total monomer concentration range is 2-8 mol/L; the cross-linking agent is N ', N' -methylene bisacrylamide, and the concentration range is 0.1-2 mol% of reaction monomer; the initiator is potassium persulfate or ammonium persulfate, and the concentration range is 0.1-2 mol% of reaction monomer; the solvent is water or dimethyl sulfoxide; the stirring temperature is 20-40 ℃, and the stirring time is 5-195 min.
Preferably, the modified high-performance fiber obtained in the step S2 is arranged in a mould in the step S4, wherein the number of layers of the modified high-performance fiber cloth is 1-15.
Preferably, the standing time in the step S4 is 15 min-6 h; the heating temperature is 45-75 ℃, and the time is 1-24 hours.
Preferably, the cleaning solution in step S5 is deionized water or a silver nitrate aqueous solution; the time for replacing the solvent is 4-10 days.
Preferably, the solvent of the silver nitrate aqueous solution is deionized water, and the concentration is 20-30 g/100 mL. Preferably, the concentration of the silver nitrate aqueous solution is 25.48g/100 mL.
Deionized water or silver nitrate water solution is selected as cleaning solution according to the system, and the deionized water is soaked in the cleaning solution to induce the generation of hydrogen bonds of the system, so that the hydrogen bond-enhanced hydrogel material is obtained; silver ions in the silver nitrate solution and amide groups of the chitosan system form an ion association effect, the ion association effect can be used as a sacrificial bond to enhance and toughen, and ions which do not participate in association in the system can be dialyzed and removed through water soaking, so that the toughness of the hydrogel is further improved.
The invention discloses an anti-impact flexible protective material in a second aspect, and the anti-impact flexible protective material prepared by the preparation method.
The hydrogel prepared by the invention has high modulus and high strength due to the energy dissipation mechanisms such as ion association, hydrogen bonds and crystallization, and the nano/micron fibers, oriented molecular chains and the like, so that the hydrogel has the advantages of high toughness, high energy consumption and the like, and has the characteristics of high Young modulus, high breaking strength and good toughness, the modulus range of the hydrogel with high toughness and high energy consumption is 20-150 MPa, the strength range is 5-50 MPa, and the energy dissipation range is 10-200 MJ/m3(ii) a Furthermore, the composite material finally prepared by the invention also has corresponding good performance.
The hydrogel has a multi-scale network structure, comprises a molecular scale structure and a phase separation scale structure, can provide a multi-level energy dissipation structure for the hydrogel, and further can enhance the energy absorption of the prepared composite material when the composite material is impacted. The hydrogel is characterized in that the phase separation structure relates to a polymer network in which one or more of monomers such as 1-vinyl imidazole, p-formylbenzoic acid, phenyl acrylate and the like participate in polymerization, the phase separation structure is a structure on a macroscopic scale in a multi-scale network structure, and the hydrogel has the characteristics of high toughness and high energy consumption due to the existence of the phase separation structure.
The high-performance fiber cloth can enable the composite material to effectively resist external destructive power; the hydrogel with high toughness and high energy consumption is used as a matrix and can generate a synergistic effect with the fiber cloth. Therefore, when the composite material prepared by the invention is damaged destructively, not only the crack of the independent hydrogel and the extraction and fracture of the fiber from the high-performance fiber cloth exist, but also the processes of peeling the surface of the high-performance fiber cloth by the hydrogel and extracting the fiber from the hydrogel matrix exist, so that the protective performance of the composite material can be effectively improved through the synergistic effect generated between the high-performance fiber cloth and the hydrogel, the deformability of the material can be maintained, and the flexible impact-resistant protective material which has good flexibility, impact resistance, stable performance and easy storage and use is obtained by compounding the high-performance fiber cloth and the hydrogel.
The invention is based on high-strength and high-modulus hydrogel with an energy dissipation mechanism (high-density hydrogen bonds, ion association, electrostatic interaction, crystalline micro-regions and the like), and has a synergistic enhancement effect with high-performance fibers, so that the composite material has an impact-resistant protection performance. Based on the deformability of the hydrogel and the fiber cloth, the fabric still keeps bendability after compounding, is easy to wear, and can be applied to individual protection and protection under other scenes.
Compared with the prior art, the invention has the following beneficial effects:
1. the impact-resistant flexible protective material is obtained by compounding the hydrogel with high toughness and high energy consumption as a matrix and the high-performance fiber cloth with high strength and high modulus as a filler. The hydrogel has a multi-scale network structure, so that the hydrogel has the characteristics of stretchability, high toughness, high energy consumption and the like, the high-performance fiber cloth has excellent hydrophilicity after surface modification, and can be compounded with the hydrogel in a pouring and curing mode to form an interaction force, so that the composite material obtained by the invention is integrally in a stable state, has the characteristics of impact resistance, bending, high energy consumption and the like, and has the advantages of low surface density, easiness in preparation, stable performance, portability, easiness in wearing and the like compared with the existing protective material.
2. The hydrogel prepared by the invention has stretchability, and compared with a metal plate, resin and foamed plastic, the flexibility and convenience of the composite protective material are more directly realized; the hydrogel/fiber cloth composite material has a multi-level energy dissipation mechanism with a multi-scale structure, so that the hydrogel/fiber cloth composite material has high strength and high toughness, and can dissipate energy when the material is impacted, so that the hydrogel/fiber cloth composite material has higher protective capability compared with a pure fiber fabric with the same areal density; the hydrogel/fiber cloth composite material is a three-dimensional polymer network containing water essentially, so that the hydrogel/fiber cloth composite material has the advantages of low density, easiness in wearing and the like compared with a metal inserting plate and a shear thickening fluid composite material.
3. The hydrogel material and the fiber cloth material are compounded in a pouring and curing mode, and the fiber cloth is subjected to surface modification to form an interaction force with the hydrogel, so that the material is integrally in a stable state, and the problems of easy phase separation, easy separation and the like in the shear thickening liquid protective material are solved.
4. The hydrogel/fiber cloth composite material can be obtained only by simple processes of solution preparation, pouring, forming and the like, and the preparation process is convenient and simple and has stronger practicability.
Drawings
FIG. 1 is a contact angle diagram of an ultra-high molecular weight polyethylene fiber cloth without surface modification;
FIG. 2 is a contact angle diagram of the ultra-high molecular weight polyethylene fiber cloth after surface modification in example 1;
FIG. 3 is a schematic side view of the composite material prepared in example 1;
FIG. 4 is a schematic diagram of a middle and small angle bending ability test of the composite material prepared in example 1;
FIG. 5 is a schematic view of a middle angle bending ability test in a bending ability test of the composite material prepared in example 1;
FIG. 6 is a schematic view of a large-angle bending ability test in a bending ability test of the composite material prepared in example 1;
FIG. 7 is a front view of the impact resistance test of the composite material prepared in example 1;
FIG. 8 is a side view of the impact resistance test of the composite material prepared in example 1;
fig. 9 is a schematic diagram showing the comparison of the performance of the hopkinson rod impact machine high-speed compression experiment of the composite material (10 layers of high-performance fiber cloth compounded by chitosan/polyacrylic acid hydrogel) prepared in example 2 and 20 layers of fiber cloth.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the present invention is not limited thereto in any way.
The solvents used in the following examples can be any of those commercially available products commonly used by those skilled in the art.
Example 1
And weaving ultrahigh molecular weight polyethylene fibers, soaking the ultrahigh molecular weight polyethylene fibers in n-hexane for 6 hours, sequentially soaking and washing the ultrahigh molecular weight polyethylene fibers by using deionized water and ethanol, and drying the ultrahigh molecular weight polyethylene fibers in a 60-DEG C blast oven for 12 hours to obtain clean and dry ultrahigh molecular weight polyethylene fiber woven cloth. In the embodiment, an ultraviolet irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber cloth is arranged in a 0.2mol/L normal hexane/acetone (7:3vol) solution of benzophenone to be soaked for 3 hours, and then the high-performance fiber cloth is taken out and placed under ultraviolet irradiation with the power of 1000W/h to irradiate the front surface and the back surface for 5 minutes respectively. And then immediately taking out and placing the fabric into acetone/water (5:5vol) mixed solution of 0.2mol/L acrylamide and 0.02mol/L N ', N' -methylene bisacrylamide for soaking for 3 hours, taking out the fabric after soaking is finished, and respectively irradiating the front surface and the back surface for 2 minutes under ultraviolet irradiation with the power of 1000W/h to finish the modification of the ultrahigh molecular weight polyethylene fiber woven fabric. And after the irradiation is finished, soaking and washing the substrate by deionized water and ethanol in sequence, and drying the substrate in a blast oven at 60 ℃ for 12 hours.
18.95mL of methacrylic acid, 1.67mL of 1-vinylimidazole, 7.850g of acrylamide, 0.45g of potassium persulfate and 0.53g N ', N' -methylenebisacrylamide, which are reaction monomers required for preparing the hydrogel, are added into 100mL of dimethyl sulfoxide solvent, and then stirred at normal temperature for 1h until the monomers are completely dissolved, so that hydrogel pre-polymerization liquid is obtained.
Cutting the modified ultra-high molecular weight polyethylene fiber woven fabric into a rectangle with the size of 150mm x 50mm, paving the rectangle in a mold with the size of 150mm x 50mm x 3mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, then putting the mold into a 65 ℃ oven, heating for 7h, curing to obtain the organic gel/fiber cloth composite material, soaking the organic gel/fiber cloth composite material in deionized water for 7 days, and changing water once every 12h to obtain the hydrogel/fiber cloth composite material.
As shown in fig. 1 and fig. 2, the contact angles of the unmodified woven fabric of ultra-high molecular weight polyethylene fiber and the modified woven fabric of ultra-high molecular weight polyethylene fiber were measured to determine the change of hydrophilicity, the unmodified contact angle was 123.1 °, it was found that the surface was hydrophobic, and the surface was completely wetted after 1min after modification, indicating that the hydrophilicity was greatly increased.
As shown in fig. 3 to 6, the 150mm by 50mm by 3mm material prepared in example 1 was bent at different angles, and it was seen that the composite material was easily bent over 180 ° only by pressing with a finger, showing excellent flexibility.
As shown in fig. 7 and 8, the steel ball air gun test was performed on the impact-resistant flexible protective material prepared in example 1, the steel ball air gun test was performed at 273.36m/s with 15 layers of fiber cloth, the total thickness of the steel ball air gun test was 4.5mm, the composite material can withstand the impact (no breakdown) of the steel ball, and the corresponding absorbed energy was about 104.61J.
The areal density of the 6-15-layer fiber cloth composite material obtained in example 1 was measured to be 0.2-0.6g/cm2Wherein the 15 layers of the fiber cloth/hydrogel composite material have the surface density of 0.54g/cm2And the cloth cover density of 15 layers of pure high-performance fibers is 0.28g/cm2。
Example 2
And weaving ultrahigh molecular weight polyethylene fibers, soaking the ultrahigh molecular weight polyethylene fibers in n-hexane for 6 hours, sequentially soaking and washing the ultrahigh molecular weight polyethylene fibers by using deionized water and ethanol, and drying the ultrahigh molecular weight polyethylene fibers in a 60-DEG C blast oven for 12 hours to obtain clean and dry ultrahigh molecular weight polyethylene fiber woven cloth. In the embodiment, an ultraviolet irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber cloth is arranged in a 0.2mol/L normal hexane/acetone (7:3vol) solution of benzophenone to be soaked for 3 hours, and then the high-performance fiber cloth is taken out and placed under ultraviolet irradiation with the power of 1000W/h to irradiate the front surface and the back surface for 5 minutes respectively. And then immediately taking out and placing the fabric in an acetone/water (5:5vol) mixed solution of 0.2mol/L acrylamide and 0.02mol/L N ', N' -methylene bisacrylamide, soaking for 3h, taking out after soaking, and respectively irradiating the front surface and the back surface for 2min under ultraviolet irradiation with the power of 1000W/h to finish the modification of the ultrahigh molecular weight polyethylene fiber woven fabric. And after the irradiation is finished, soaking and washing the substrate by deionized water and ethanol in sequence, and drying the substrate in a blast oven at 60 ℃ for 12 hours.
Adding 5g of chitosan and 12.5g of acrylic acid serving as reaction monomers into 32.5g of deionized water, violently stirring for 3h until the chitosan and the acrylic acid are completely dissolved, adding 0.125g of initiator ammonium persulfate, stirring again for 15min until the ammonium persulfate is dissolved, and then placing the mixture into a centrifugal machine to perform centrifugal degassing for 5min at the rotating speed of 10000r/min to obtain the hydrogel pre-polymerization liquid.
Cutting the modified ultra-high molecular weight polyethylene fiber woven cloth into a rectangle with the length of 30mm x 40mm, spreading the rectangle in a mold with the length of 30mm x 40mm x 5mm, pouring the hydrogel prepolymerization solution into the mold, pressurizing and standing for about 6 hours until the fiber cloth is completely soaked, and then placing the fiber cloth in an oven with the temperature of 50 ℃ for heating and curing for 24 hours. And after the curing is completed, soaking the fiber cloth in silver nitrate aqueous solution prepared from 25.48g of silver nitrate and 100ml of deionized water, soaking the fiber cloth in the silver nitrate aqueous solution in the dark for 7 days, and then soaking the fiber cloth in the deionized water for 1 day to obtain the hydrogel/fiber cloth composite material.
As shown in fig. 9, when a hopkinson rod impact machine high-speed compression experiment was performed on the composite material (chitosan/polyacrylic acid hydrogel composite 10-layer fiber cloth) prepared in example 2 and 20-layer fiber cloth, it can be seen from a comparison graph of the experiment results that the strength of the composite material reaches 12.3MPa and the strength of the pure fiber cloth is only 6.4MPa, and it can be seen that the strength of the obtained composite material is greatly increased and almost doubled as much as the strength of the pure fiber cloth.
Example 3
And weaving ultrahigh molecular weight polyethylene fibers, soaking the ultrahigh molecular weight polyethylene fibers in n-hexane for 6 hours, sequentially soaking and washing the ultrahigh molecular weight polyethylene fibers by using deionized water and ethanol, and drying the ultrahigh molecular weight polyethylene fibers in a 60-DEG C blast oven for 12 hours to obtain clean and dry ultrahigh molecular weight polyethylene fiber woven cloth. In the embodiment, an ultraviolet irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber cloth is arranged in a 0.2mol/L normal hexane/acetone (7:3vol) solution of benzophenone to be soaked for 3 hours, and then the high-performance fiber cloth is taken out and placed under ultraviolet irradiation with the power of 1000W/h to irradiate the front surface and the back surface for 5 minutes respectively. And then immediately taking out and placing the fabric in an acetone/water (5:5vol) mixed solution of 0.2mol/L acrylamide and 0.02mol/L N ', N' -methylene bisacrylamide, soaking for 3h, taking out after soaking, and respectively irradiating the front surface and the back surface for 2min under ultraviolet irradiation with the power of 1000W/h to finish the modification of the ultrahigh molecular weight polyethylene fiber woven fabric. And after the irradiation is finished, soaking and washing the substrate by deionized water and ethanol in sequence, and drying the substrate in a blast oven at 60 ℃ for 12 hours.
2.68g of sodium styrene sulfonate, 2.65g of methacrylyl propyl trimethyl ammonium chloride, 0.0290g of initiator ammonium persulfate and 0.0039g N ', N' -methylene bisacrylamide as well as 0.29g of sodium chloride serving as a dissolution promoter (which destroys the charge balance in the solution and promotes the dissolution of the monomers) are dissolved in 7.35g of water, stirred for 30min at room temperature and centrifuged for 5min at 10000r/min to remove gas, thus obtaining the hydrogel prepolymer solution.
Cutting the modified ultra-high molecular weight polyethylene fiber woven fabric into a rectangle with the length of 30mm x 40mm, paving the rectangle in a mold with the length of 30mm x 40mm x 5mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, then putting the fiber cloth into a 50 ℃ oven to be heated for 24h for curing, and then soaking the fiber cloth in deionized water for 7 days to obtain the hydrogel/fiber cloth composite material.
Example 4
And (3) soaking the Kevlar fiber woven fabric in n-hexane for 6h, sequentially soaking and washing the Kevlar fiber woven fabric by deionized water and ethanol, and drying the Kevlar fiber woven fabric in a 60-DEG C blast oven for 12h to obtain clean and dry Kevlar fiber woven fabric. In the embodiment, an ultraviolet irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber cloth is arranged in a 0.2mol/L normal hexane/acetone (7:3vol) solution of benzophenone to be soaked for 3 hours, and then the high-performance fiber cloth is taken out and placed under ultraviolet irradiation with the power of 1000W/h to irradiate the front surface and the back surface for 5 minutes respectively. And then immediately taking out the fabric and placing the fabric in an acetone/water (5:5vol) mixed solution of 0.2mol/L acrylamide and 0.02mol/L N ', N' -methylene bisacrylamide for soaking for 3 hours, taking out the fabric after soaking and respectively irradiating the front surface and the back surface for 2 minutes under ultraviolet irradiation with the power of 1000W/h, and finishing the modification of the Kevlar fiber woven fabric. And after the irradiation is finished, soaking and washing the substrate by deionized water and ethanol in sequence, and drying the substrate in a blast oven at 60 ℃ for 12 hours.
18.95mL of methacrylic acid, 1.67mL of 1-vinylimidazole, 7.850g of acrylamide, 0.45g of potassium persulfate and 0.53g N ', N' -methylenebisacrylamide, which are reaction monomers required for preparing the hydrogel, are added into 100mL of dimethyl sulfoxide solvent, and then stirred for 1h at normal temperature until the monomers are completely dissolved, so that hydrogel pre-polymerization liquid is obtained.
Cutting the modified Kevlar fiber woven cloth into a rectangle with the size of 150mm x 50mm, paving the rectangle in a mold with the size of 150mm x 50mm x 3mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, putting the mold into a 65 ℃ oven, heating for 7h, curing to obtain the organic gel/fiber cloth composite material, soaking the organic gel/fiber cloth composite material in deionized water for 7 days, and changing water once every 12h to obtain the hydrogel/fiber cloth composite material.
Example 5
And weaving ultrahigh molecular weight polyethylene fibers, soaking the ultrahigh molecular weight polyethylene fibers in n-hexane for 6 hours, sequentially soaking and washing the ultrahigh molecular weight polyethylene fibers by using deionized water and ethanol, and drying the ultrahigh molecular weight polyethylene fibers in a 60-DEG C blast oven for 12 hours to obtain clean and dry ultrahigh molecular weight polyethylene fiber woven cloth. In the embodiment, a plasma irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber is arranged in a plasma oxygen atmosphere of 300W to irradiate the front surface and the back surface for 5min respectively, and then the high-performance fiber cloth is immediately placed in an aqueous solution (the pH value of the acetic acid is adjusted to 3-4) of a silane coupling agent KH-570 by weight percent and soaked for 12h, so that the modified ultrahigh molecular weight polyethylene fiber woven cloth is obtained. And then soaking and washing the mixture by deionized water and ethanol in sequence, and drying the mixture in a blast oven at 60 ℃ for 12 hours.
18.95mL of methacrylic acid, 1.67mL of 1-vinylimidazole, 7.850g of acrylamide, 0.45g of potassium persulfate and 0.53g N ', N' -methylenebisacrylamide, which are reaction monomers required for preparing the hydrogel, are added into 100mL of dimethyl sulfoxide solvent, and then stirred for 1h at normal temperature until the monomers are completely dissolved, so that hydrogel pre-polymerization liquid is obtained.
Cutting the modified ultra-high molecular weight polyethylene fiber woven fabric into a rectangle with the size of 150mm x 50mm, paving the rectangle in a mold with the size of 150mm x 50mm x 3mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, putting the mold into a 65 ℃ oven, heating for 7h, curing to obtain the organic gel/fiber cloth composite material, soaking the organic gel/fiber cloth composite material in deionized water for 7 days, and changing water once every 12h to obtain the hydrogel/fiber cloth composite material.
Example 6
And weaving ultrahigh molecular weight polyethylene fibers, soaking the ultrahigh molecular weight polyethylene fibers in n-hexane for 6 hours, sequentially soaking and washing the ultrahigh molecular weight polyethylene fibers by using deionized water and ethanol, and drying the ultrahigh molecular weight polyethylene fibers in a 60-DEG C blast oven for 12 hours to obtain clean and dry ultrahigh molecular weight polyethylene fiber woven cloth. In the embodiment, a chemical reagent treatment method is adopted to modify the high-performance fiber cloth, and the chromic acid etching solution is prepared by mixing potassium dichromate, sulfuric acid and distilled water according to the mass ratio of 7:150: 12. And (3) arranging the high-performance fiber in an etching solution, treating for 1-2 min, sequentially soaking and washing with deionized water and ethanol, and placing in a 60 ℃ oven for vacuum drying for 12 h.
18.95mL of methacrylic acid, 1.67mL of 1-vinylimidazole, 7.850g of acrylamide, 0.45g of potassium persulfate and 0.53g N ', N' -methylenebisacrylamide, which are reaction monomers required for preparing the hydrogel, are added into 100mL of dimethyl sulfoxide solvent, and then stirred for 1h at normal temperature until the monomers are completely dissolved, so that hydrogel pre-polymerization liquid is obtained.
Cutting the modified ultra-high molecular weight polyethylene fiber woven fabric into a rectangle with the size of 150mm x 50mm, paving the rectangle in a mold with the size of 150mm x 50mm x 3mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, putting the mold into a 65 ℃ oven, heating for 7h, curing to obtain the organic gel/fiber cloth composite material, soaking the organic gel/fiber cloth composite material in deionized water for 7 days, and changing water once every 12h to obtain the hydrogel/fiber cloth composite material.
Example 7
And weaving ultrahigh molecular weight polyethylene fibers, soaking the ultrahigh molecular weight polyethylene fibers in n-hexane for 6 hours, sequentially soaking and washing the ultrahigh molecular weight polyethylene fibers by using deionized water and ethanol, and drying the ultrahigh molecular weight polyethylene fibers in a 60-DEG C blast oven for 12 hours to obtain clean and dry ultrahigh molecular weight polyethylene fiber woven cloth. In the embodiment, a plasma irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber is arranged in a plasma oxygen atmosphere of 300W to irradiate the front surface and the back surface for 5min respectively, and then the high-performance fiber cloth is immediately placed in an aqueous solution (the pH value of the acetic acid is adjusted to 3-4) of a silane coupling agent KH-570 by weight percent and soaked for 12h, so that the modified ultrahigh molecular weight polyethylene fiber woven cloth is obtained. And then soaking and washing the mixture by deionized water and ethanol in sequence, and drying the mixture in a blast oven at 60 ℃ for 12 hours.
Adding 5g of chitosan and 12.5g of acrylic acid serving as reaction monomers into 32.5g of deionized water, violently stirring for 3h until the chitosan and the acrylic acid are completely dissolved, adding 0.125g of initiator ammonium persulfate, stirring again for 15min until the ammonium persulfate is dissolved, and then placing the mixture into a centrifugal machine to perform centrifugal degassing for 5min at the rotating speed of 10000r/min to obtain the hydrogel pre-polymerization liquid.
Cutting the modified ultra-high molecular weight polyethylene fiber woven cloth into a rectangle with the length of 30mm x 40mm, spreading the rectangle in a mold with the length of 30mm x 40mm x 5mm, pouring the hydrogel prepolymerization solution into the mold, pressurizing and standing for about 6 hours until the fiber cloth is completely soaked, and then placing the fiber cloth in an oven with the temperature of 50 ℃ for heating and curing for 24 hours. And after the curing is completed, soaking the fiber cloth in silver nitrate aqueous solution prepared from 25.48g of silver nitrate and 100ml of deionized water, soaking the fiber cloth in the dark for 7 days, and then soaking the fiber cloth in the deionized water for 1 day to obtain the hydrogel/fiber cloth composite material.
Example 8
And (3) soaking the Kevlar fiber woven fabric in n-hexane for 6h, sequentially soaking and washing the Kevlar fiber woven fabric by deionized water and ethanol, and drying the Kevlar fiber woven fabric in a 60-DEG C blast oven for 12h to obtain clean and dry Kevlar fiber woven fabric. In the embodiment, a chemical reagent treatment method is adopted to modify the high-performance fiber cloth, and the chromic acid etching solution is prepared by mixing potassium dichromate, sulfuric acid and distilled water according to the mass ratio of 7:150: 12. And (3) arranging the high-performance fiber in an etching solution, treating for 1-2 min, sequentially soaking and washing with deionized water and ethanol, and placing in a 60 ℃ oven for vacuum drying for 12 h.
1.825mL of methacrylic acid, 0.1625mL of 1-vinylimidazole, 0.785g of acrylamide, 0.045g of potassium persulfate and 0.053g N ', N' -methylenebisacrylamide which are reaction monomers required for preparing the hydrogel are added into a reaction bottle filled with 100mL of dimethyl sulfoxide, and the reaction bottle is stirred at normal temperature for 1h until all the reaction monomers are dissolved, so that hydrogel pre-polymerization liquid is obtained.
Cutting the modified Kevlar fiber woven cloth into a rectangle with the size of 30mm x 40mm, paving the rectangle in a mold with the size of 30mm x 40mm x 5mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, putting the mold into a 65 ℃ oven, heating for 7h, curing to obtain the organic gel/fiber cloth composite material, soaking the organic gel/fiber cloth composite material in deionized water for 7 days, and changing water once every 12h to obtain the hydrogel/fiber cloth composite material.
Example 9
And weaving ultrahigh molecular weight polyethylene fibers, soaking the ultrahigh molecular weight polyethylene fibers in n-hexane for 6 hours, sequentially soaking and washing the ultrahigh molecular weight polyethylene fibers by using deionized water and ethanol, and drying the ultrahigh molecular weight polyethylene fibers in a 60-DEG C blast oven for 12 hours to obtain clean and dry ultrahigh molecular weight polyethylene fiber woven cloth. In the embodiment, a plasma irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber is arranged in a plasma oxygen atmosphere of 300W to irradiate the front surface and the back surface for 5min respectively, and then the high-performance fiber cloth is immediately placed in an aqueous solution (the pH value of the acetic acid is adjusted to 3-4) of a silane coupling agent KH-570 by weight percent and soaked for 12h, so that the modified ultrahigh molecular weight polyethylene fiber woven cloth is obtained. And then soaking and washing the mixture by deionized water and ethanol in sequence, and drying the mixture in a blast oven at 60 ℃ for 12 hours.
2.68g of styrene sodium sulfonate, 2.65g of methacryl propyl trimethyl ammonium chloride, 0.0290g of initiator ammonium persulfate and 0.0039g of cross-linking agent N ', N' -methylene bisacrylamide are added, 0.29g of sodium chloride serving as a dissolving promoter (which destroys charge balance in the solution and promotes dissolution of the monomers) is dissolved in 7.35g of water, stirred for 30min at room temperature and centrifuged for 5min at 10000r/min to remove gas, and the hydrogel pre-polymerization solution is obtained.
Cutting the modified ultra-high molecular weight polyethylene fiber woven fabric into a rectangle with the length of 30mm x 40mm, paving the rectangle in a mold with the length of 30mm x 40mm x 5mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, then putting the fiber cloth into a 50 ℃ oven to be heated for 24h for curing, and then soaking the fiber cloth in deionized water for 7 days to obtain the hydrogel/fiber cloth composite material.
Example 10
And weaving ultrahigh molecular weight polyethylene fibers, soaking the ultrahigh molecular weight polyethylene fibers in n-hexane for 6 hours, sequentially soaking and washing the ultrahigh molecular weight polyethylene fibers by using deionized water and ethanol, and drying the ultrahigh molecular weight polyethylene fibers in a 60-DEG C blast oven for 12 hours to obtain clean and dry ultrahigh molecular weight polyethylene fiber woven cloth. In the embodiment, a plasma irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber is arranged in a plasma oxygen atmosphere of 300W to irradiate the front surface and the back surface for 5min respectively, and then the high-performance fiber cloth is immediately placed in an aqueous solution (the pH value of the acetic acid is adjusted to 3-4) of a silane coupling agent KH-570 by weight percent and soaked for 12h, so that the modified ultrahigh molecular weight polyethylene fiber woven cloth is obtained. Then soaking and washing the mixture by deionized water and ethanol in sequence, and drying the mixture in a blast oven at 60 ℃ for 12 hours.
1.825mL of methacrylic acid, 0.1625mL of 1-vinylimidazole, 0.785g of acrylamide, 0.045g of potassium persulfate and 0.053g N ', N' -methylenebisacrylamide which are reaction monomers required for preparing the hydrogel are added into a reaction bottle filled with 100mL of dimethyl sulfoxide, and the reaction bottle is stirred at normal temperature for 1h until all the reaction monomers are dissolved, so that hydrogel pre-polymerization liquid is obtained.
Cutting the modified ultra-high molecular weight polyethylene fiber woven fabric into a rectangle with the size of 30mm x 40mm, paving the rectangle in a mold with the size of 30mm x 40mm x 5mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, putting the mold into a 65 ℃ oven, heating for 7h, curing to obtain the organic gel/fiber cloth composite material, soaking the organic gel/fiber cloth composite material in deionized water for 7 days, and changing water once every 12h to obtain the hydrogel/fiber cloth composite material.
Example 11
And (3) arranging the ultrahigh molecular weight polyethylene fibers in a one-way manner in n-hexane, soaking for 6h, sequentially soaking and washing by deionized water and ethanol, and then drying in a 60 ℃ blast oven for 12h to obtain clean and dry ultrahigh molecular weight polyethylene fiber one-way cloth. In the embodiment, an ultraviolet irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber cloth is arranged in a 0.2mol/L normal hexane/acetone (7:3vol) solution of benzophenone to be soaked for 3 hours, and then the high-performance fiber cloth is taken out and placed under ultraviolet irradiation with the power of 1000W/h to irradiate the front surface and the back surface for 5 minutes respectively. And then immediately taking out and placing the fabric into acetone/water (5:5vol) mixed solution of 0.2mol/L acrylamide and 0.02mol/L N ', N' -methylene bisacrylamide for soaking for 3 hours, taking out the fabric after soaking is finished, and respectively irradiating the front surface and the back surface for 2 minutes under ultraviolet irradiation with the power of 1000W/h to finish the modification of the ultrahigh molecular weight polyethylene fiber unidirectional fabric. And after the irradiation is finished, soaking and washing the substrate by deionized water and ethanol in sequence, and drying the substrate in a blast oven at 60 ℃ for 12 hours.
18.95mL of methacrylic acid, 1.67mL of 1-vinylimidazole, 7.850g of acrylamide, 0.45g of potassium persulfate and 0.53g N ', N' -methylenebisacrylamide, which are reaction monomers required for preparing the hydrogel, are added into 100mL of dimethyl sulfoxide solvent, and then stirred at normal temperature for 1h until the monomers are completely dissolved, so that hydrogel pre-polymerization liquid is obtained.
Cutting the modified ultrahigh molecular weight polyethylene fiber unidirectional cloth into a rectangle with the length of 150mm x 50mm, paving the rectangle in a mold with the length of 150mm x 50mm x 3mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, then putting the mold into a 65 ℃ oven, heating for 7h, curing to obtain the organic gel/fiber cloth composite material, soaking the organic gel/fiber cloth composite material in deionized water for 7 days, and changing water once every 12h to obtain the hydrogel/fiber cloth composite material.
Example 12
And (3) soaking the carbon fiber in n-hexane for 6h, sequentially soaking and washing the carbon fiber by deionized water and ethanol, and drying the carbon fiber in a 60 ℃ blast oven for 12h to obtain clean and dry carbon fiber cloth. In the embodiment, an ultraviolet irradiation grafting method is adopted to modify high-performance fiber cloth, the obtained high-performance fiber cloth is arranged in a 0.2mol/L normal hexane/acetone (7:3vol) solution of benzophenone to be soaked for 3 hours, and then the high-performance fiber cloth is taken out and placed under ultraviolet irradiation with the power of 1000W/h to irradiate the front surface and the back surface for 5 minutes respectively. And then immediately taking out and placing the carbon fiber cloth into a mixed solution of 0.2mol/L acrylamide and 0.02mol/L N ', N' -methylene bisacrylamide in acetone/water (5:5vol) for soaking for 3 hours, taking out after soaking is finished, and respectively irradiating the front surface and the back surface for 2 minutes under ultraviolet irradiation with the power of 1000W/h to finish the modification of the carbon fiber cloth. And after the irradiation is finished, soaking and washing the substrate by deionized water and ethanol in sequence, and drying the substrate in a blast oven at 60 ℃ for 12 hours.
18.95mL of methacrylic acid, 1.67mL of 1-vinylimidazole, 7.850g of acrylamide, 0.45g of potassium persulfate and 0.53g N ', N' -methylenebisacrylamide, which are reaction monomers required for preparing the hydrogel, are added into 100mL of dimethyl sulfoxide solvent, and then stirred at normal temperature for 1h until the monomers are completely dissolved, so that hydrogel pre-polymerization liquid is obtained.
Cutting the modified carbon fiber cloth into a rectangle with the size of 150mm x 50mm, paving the rectangle in a mold with the size of 150mm x 50mm x 3mm, pouring the hydrogel prepolymerization solution into the mold, standing for about 30min until the fiber cloth is completely soaked, then putting the mold into a 65 ℃ oven, heating for 7h, curing to obtain the organogel/fiber cloth composite material, soaking the organogel/fiber cloth composite material in deionized water for 7 days, and changing water once every 12h to obtain the hydrogel/fiber cloth composite material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The preparation method of the impact-resistant flexible protective material is characterized by comprising the following steps of:
s1: carrying out surface modification treatment on the high-performance fiber cloth to obtain modified high-performance fiber cloth;
s2: cleaning and drying the modified high-performance fiber cloth obtained in the step S1;
s3: adding a reaction monomer, a cross-linking agent and an initiator into a solvent, and stirring until the reaction monomer, the cross-linking agent and the initiator are completely dissolved to obtain a hydrogel pre-polymerization solution;
s4: arranging the modified high-performance fiber obtained in the step S2 in a mold, injecting the hydrogel pre-polymerization liquid obtained in the step S3 into the mold, standing until the modified high-performance fiber cloth is completely soaked, and heating to initiate polymerization reaction to obtain a hydrogel/fiber cloth composite material or an organogel/fiber cloth composite material;
s5: and (4) soaking the hydrogel/fiber cloth composite material or the organic gel/fiber cloth composite material obtained in the step (S4) in a cleaning solution, replacing the solvent, and completely replacing to obtain the impact-resistant flexible protective material.
2. The method for preparing an impact-resistant flexible protective material according to claim 1, wherein the high-performance fiber cloth in step S1 is an ultra-high molecular weight polyethylene fiber woven cloth, an ultra-high molecular weight polyethylene fiber unidirectional cloth, a kevlar fiber woven cloth or a carbon fiber cloth.
3. The method for preparing an impact-resistant flexible protective material according to claim 1, wherein the surface modification treatment in step S1 is a chemical agent treatment method, an ultraviolet irradiation grafting method, a plasma irradiation method or a high-energy ray irradiation method.
4. The method for preparing an impact-resistant flexible protective material according to claim 1, wherein the cleaning and drying in step S2 is to sequentially soak and wash the high-performance fiber cloth with deionized water and ethanol, and then dry the high-performance fiber cloth in an oven at 60 ℃ for 1-24 hours.
5. The preparation method of an impact-resistant flexible protective material according to claim 1, wherein the reactive monomer in step S3 is one or more of 1-vinylimidazole, methacrylic acid, acrylamide, chitosan, acrylic acid, sodium styrene sulfonate and methacryl propyl trimethyl ammonium chloride, and the total monomer concentration range is 2 to 8 mol/L; the cross-linking agent is N ', N' -methylene bisacrylamide, and the concentration range is 0.1-2 mol% of reaction monomer; the initiator is potassium persulfate or ammonium persulfate, and the concentration range is 0.1-2 mol% of reaction monomer; the solvent is water or dimethyl sulfoxide; the stirring temperature is 20-40 ℃, and the stirring time is 5-195 min.
6. The method for preparing an impact-resistant flexible protective material according to claim 1, wherein the modified high-performance fiber obtained in step S2 is arranged in a mold in step S4, and the number of layers of the modified high-performance fiber cloth is 1-15.
7. The method for preparing an impact-resistant flexible protective material according to claim 1, wherein the standing time in step S4 is 15min to 6 h; the heating temperature is 45-75 ℃, and the time is 1-24 hours.
8. The method for preparing an impact-resistant flexible protective material according to claim 1, wherein the cleaning solution in step S5 is deionized water or a silver nitrate aqueous solution; the time for replacing the solvent is 4-10 days.
9. The preparation method of the impact-resistant flexible protective material according to claim 8, wherein the solvent of the silver nitrate aqueous solution is deionized water, and the concentration is 20-30 g/100 mL.
10. An impact-resistant flexible protective material, which is prepared by the preparation method of any one of claims 1 to 9.
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