High-toughness antifouling antibacterial hydrogel and preparation method thereof

Abstract

The invention belongs to the field of hydrogel, and particularly relates to high-toughness antifouling antibacterial hydrogel and a preparation method thereof. The high-toughness antifouling antibacterial hydrogel provided by the invention is prepared by mixing polyvinyl alcohol, betaine methacrylate sulfonate, a MoS2 loaded cellulose nanofiber composite material, a mesoporous material loaded with a bactericide, sulfuric acid, an initiator and water and then performing freeze thawing treatment. According to the preparation method, the mesoporous material loaded with the bactericide and the MoS2 loaded cellulose nanofiber composite material are introduced into the hydrogel, so that the anti-adhesion performance, the bactericidal performance and the mechanical performance of the hydrogel are greatly improved. According to the invention, the problems of single antifouling mechanism and poor mechanical property of the traditional hydrogel are solved by constructing a hydrogel system of anti-adhesion, sterilization and mechanical property enhancement, and a good solution is provided for long-acting antifouling of marine equipment.

Description

Technical Field

[0001] This invention belongs to the field of hydrogels, and particularly relates to a high-toughness antifouling and antibacterial hydrogel and its preparation method. Background Technology

[0002] Marine biofouling refers to the phenomenon where marine microorganisms (such as bacteria and algae), plants and animals (such as barnacles and shellfish), and other organisms attach to and proliferate on the surfaces of ships, subsea equipment, drilling platforms, and other structures. This phenomenon causes multiple hazards: acidic substances secreted by the attached organisms accelerate metal corrosion, shortening equipment lifespan; roughening of the hull surface increases navigation resistance, potentially increasing fuel consumption by up to 40%; the biofouling layer covering sensors interferes with signal transmission; and traditional antifouling methods relying on toxic chemical biocides (such as organotin and copper-based compounds) have been gradually restricted by international conventions due to severe pollution of the marine ecosystem. Marine organisms tend to attach to hard surfaces to gain survival advantages (such as avoiding predators and obtaining nutrients), and human-made marine engineering facilities conveniently provide such habitats.

[0003] Due to the presence of a surface hydration layer, antifouling gels possess certain antifouling properties and have promising applications in the field of marine equipment corrosion protection. However, traditional antifouling gels suffer from a single antifouling mechanism and poor mechanical properties, which to some extent limits their application in the field of marine equipment corrosion protection. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a high-toughness antifouling and antibacterial hydrogel and its preparation method. This invention solves the problems of the single antifouling mechanism and poor mechanical properties of traditional hydrogels by constructing a hydrogel system of "anti-adhesion-bactericidal-enhanced mechanical properties", and provides a good solution for long-term antifouling of marine equipment.

[0005] This invention provides a high-toughness antifouling and antibacterial hydrogel, which is made by mixing polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-loaded cellulose nanofiber composite material, mesoporous material loaded with bactericide, sulfuric acid, initiator and water, and then subjecting it to freeze-thaw treatment.

[0006] Preferably, the amount of the MoS2-loaded cellulose nanofiber composite material is 0.05 to 1.5 wt% of the total mass of polyvinyl alcohol and betaine sulfonate methacrylate.

[0007] Preferably, the bactericide in the mesoporous material loaded with the bactericide is one or more of bromopyrrolidone, iodopyridinol, chitosan quaternary ammonium salt, and benzisothiazolinone; the mesoporous material in the mesoporous material loaded with the bactericide is mesoporous silica.

[0008] Preferably, the amount of the mesoporous material loaded with the bactericide is 5 to 20 wt% of the total mass of polyvinyl alcohol and betaine sulfonate methacrylate.

[0009] Preferably, the initiator is one or more of potassium persulfate, ammonium persulfate, and sodium persulfate.

[0010] Preferably, the mass ratio of polyvinyl alcohol, betaine methacrylate sulfonate, sulfuric acid and initiator is 1.2:(0.4-0.8):(0.5-1):(0.004-0.008).

[0011] This invention provides a method for preparing the high-toughness antifouling and antibacterial hydrogel described above, comprising the following steps:

[0012] Polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-loaded cellulose nanofiber composite material, mesoporous material loaded with bactericide, sulfuric acid, initiator and water were mixed to obtain a hydrogel prepolymer solution.

[0013] The hydrogel prepolymer solution was subjected to freeze-thaw treatment to obtain a high-toughness antifouling and antibacterial hydrogel.

[0014] Preferably, the mixing process specifically includes:

[0015] Polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-supported cellulose nanofiber composite material, sulfuric acid and water were mixed to obtain a mixture.

[0016] A mesoporous material loaded with a bactericide, an initiator, and the mixture are combined to obtain a hydrogel prepolymer.

[0017] Preferably, the MoS2-supported cellulose nanofiber composite material is prepared according to the following steps:

[0018] MoS2-loaded cellulose nanofiber composite material was obtained by mixing molybdenum disulfide with an aqueous solution of cellulose nanofibers and then subjecting the mixture to ultrasonic treatment.

[0019] Preferably, the mesoporous material loaded with the bactericide is prepared according to the following steps:

[0020] The bactericide and mesoporous material are mixed in a liquid medium, and the liquid medium is removed to obtain a mesoporous material loaded with the bactericide.

[0021] Compared with existing technologies, this invention provides a high-toughness antifouling and antibacterial hydrogel and its preparation method. The high-toughness antifouling and antibacterial hydrogel provided by this invention is prepared by mixing polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-loaded cellulose nanofiber composite material, a mesoporous material loaded with a bactericide, sulfuric acid, an initiator, and water, followed by freeze-thaw treatment. This invention significantly improves the anti-adhesion, bactericidal, and mechanical properties of the hydrogel by introducing a mesoporous material loaded with a bactericide and a MoS2-loaded cellulose nanofiber composite material into the hydrogel. By constructing an "anti-adhesion-bactericidal-enhanced mechanical properties" hydrogel system, this invention solves the problems of the single antifouling mechanism and poor mechanical properties of traditional hydrogels, providing a good solution for long-term antifouling of marine equipment. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0023] Figure 1 These are the TEM morphology images and EDS mapping images of MoS2@CNF provided in Embodiment 1 of the present invention for Mo and S elements.

[0024] Figure 2 This is a tensile strain-stress curve of the hydrogel provided in Embodiment 6 of the present invention;

[0025] Figure 3 This is a tensile strength diagram of the hydrogel provided in Embodiment 6 of the present invention;

[0026] Figure 4 This is a diagram showing the tensile toughness values ​​of the hydrogel provided in Embodiment 6 of the present invention;

[0027] Figure 5 This is a compression strain-stress curve of the hydrogel provided in Embodiment 6 of the present invention;

[0028] Figure 6 This is a diagram showing the compressive strength of the hydrogel provided in Embodiment 6 of the present invention;

[0029] Figure 7 This is a diagram showing the compressive toughness values ​​of the hydrogel provided in Embodiment 6 of the present invention;

[0030] Figure 8 This is a fluorescence microscope image of the anti-BSA adhesion experiment of the hydrogel provided in Example 6 of the present invention;

[0031] Figure 9This is a BSA coverage diagram of the hydrogel provided in Embodiment 6 of the present invention;

[0032] Figure 10 This is an experimental diagram of the hydrogel's resistance to Chlorella adhesion provided in Embodiment 6 of the present invention;

[0033] Figure 11 This is a diagram showing the Chlorella coverage rate of the hydrogel provided in Embodiment 6 of the present invention;

[0034] Figure 12 These are optical photographs of the antibacterial properties of different materials against Escherichia coli and Staphylococcus aureus under and without near-infrared light irradiation, provided in Embodiment 6 of the present invention.

[0035] Figure 13 This is a graph showing the inhibition rates of different materials against Escherichia coli and Staphylococcus aureus under near-infrared light irradiation, as provided in Embodiment 6 of the present invention.

[0036] Figure 14 These are real photos taken after the hydrogel provided in Embodiment 6 of the present invention underwent a 90-day sea test in Haikou Bay;

[0037] Figure 15 This is a dirt coverage diagram of the hydrogel provided in Embodiment 6 of the present invention. Detailed Implementation

[0038] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] This invention provides a high-toughness antifouling and antibacterial hydrogel, which is made by mixing polyvinyl alcohol, betaine methacrylate sulfonate (SBMA), MoS2-loaded cellulose nanofiber composite material (MoS2@CNF), mesoporous material loaded with bactericide, sulfuric acid, initiator and water, and then subjecting it to freeze-thaw treatment.

[0040] In the hydrogel provided by the present invention, the mass ratio of polyvinyl alcohol to betaine sulfonate methacrylate is preferably 1.2:(0.4-0.8), specifically 1.2:0.4, 1.2:0.45, 1.2:0.5, 1.2:0.55, 1.2:0.6, 1.2:0.65, 1.2:0.7, 1.2:0.75 or 1.2:0.8.

[0041] In the hydrogel provided by the present invention, the MoS2-loaded cellulose nanofiber composite material is preferably prepared by ultrasonically exfoliating blocky molybdenum disulfide in an aqueous solution of cellulose nanofibers (CNF).

[0042] In the hydrogel provided by the present invention, the amount of the MoS2-supported cellulose nanofiber composite material is preferably 0.05 to 1.5 wt% of the total mass of polyvinyl alcohol and betaine sulfonate methacrylate, specifically 0.05 wt%, 0.07 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, or 1.5 wt%.

[0043] In the hydrogel provided by the present invention, the bactericide in the mesoporous material loaded with bactericide is preferably one or more of bromopyrrolidone, iodopyridinol, chitosan quaternary ammonium salt and benzisothiazolinone; the mesoporous material in the mesoporous material loaded with bactericide is preferably mesoporous silica.

[0044] In the hydrogel provided by the present invention, the amount of the mesoporous material loaded with bactericide is preferably 5 to 20 wt% of the total mass of polyvinyl alcohol and betaine sulfonate methacrylate, specifically 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%.

[0045] In the hydrogel provided by the present invention, the mass ratio of sulfuric acid to polyvinyl alcohol is preferably (0.5-1):1.2, specifically 0.5:1.2, 0.52:1.2, 0.55:1.2, 0.57:1.2, 0.6:1.2, 0.62:1.2, 0.65:1.2, 0.67:1.2, 0.7:1.2, 0.72:1.2, 0.75:1.2, 0.77:1.2, 0.8:1.2, 0.82:1.2, 0.85:1.2, 0.87:1.2, 0.9:1.2, 0.92:1.2, 0.95:1.2, 0.97:1.2, or 1:1.2.

[0046] In the hydrogel provided by the present invention, the initiator is preferably one or more of potassium persulfate (KPS), ammonium persulfate and sodium persulfate.

[0047] In the hydrogel provided by the present invention, the mass ratio of the initiator to polyvinyl alcohol is preferably (0.004-0.008):1.2, specifically 0.004:1.2, 0.0042:1.2, 0.0045:1.2, 0.0047:1.2, 0.005:1.2, 0.0052:1.2, 0.0055:1.2, 0.0057:1.2, 0.006:1.2, 0.0062:1.2, 0.0065:1.2, 0.0067:1.2, 0.007:1.2, 0.0072:1.2, 0.0075:1.2, 0.0077:1.2, or 0.008:1.2.

[0048] In the hydrogel provided by the present invention, the preferred mass ratio of water to polyvinyl alcohol is (5-15):1.2, specifically 5:1.2, 5.5:1.2, 6:1.2, 6.5:1.2, 7:1.2, 7.5:1.2, 8:1.2, 8.5:1.2, 9:1.2, 9.5:1.2, 10:1.2, 10.5:1.2, 11:1.2, 11.5:1.2, 12:1.2, 12.5:1.2, 13:1.2, 13.5:1.2, 14:1.2, 14.5:1.2, or 15:1.2.

[0049] In the hydrogel provided by this invention, the freezing temperature of the freeze-thaw treatment is preferably -30 to -50°C, specifically -30°C, -35°C, -40°C, -45°C, or -50°C; the freezing time (per cycle) of the freeze-thaw treatment is preferably 8 to 16 hours, specifically 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, or 16 hours; the thawing temperature of the freeze-thaw treatment is preferably 20 to 40°C, specifically 20°C, 25°C, 30°C, 35°C, or 40°C; the thawing time (per cycle) of the freeze-thaw treatment is preferably 8 to 16 hours, specifically 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, or 16 hours; and the number of freeze-thaw cycles of the freeze-thaw treatment is preferably 1 to 5 times, specifically 1 time, 2 times, 3 times, 4 times, or 5 times.

[0050] This invention also provides a method for preparing the high-toughness antifouling and antibacterial hydrogel described in the above technical solution, comprising the following steps:

[0051] Polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-loaded cellulose nanofiber composite material, mesoporous material loaded with bactericide, sulfuric acid, initiator and water were mixed to obtain a hydrogel prepolymer solution.

[0052] The hydrogel prepolymer solution was subjected to freeze-thaw treatment to obtain a high-toughness antifouling and antibacterial hydrogel.

[0053] In the preparation method provided by the present invention, the MoS2-supported cellulose nanofiber composite material is preferably prepared according to the following steps:

[0054] MoS2-loaded cellulose nanofiber composite material was obtained by mixing molybdenum disulfide with an aqueous solution of cellulose nanofibers and then subjecting the mixture to ultrasonic treatment.

[0055] In the preparation steps of the MoS2-supported cellulose nanofiber composite material provided by the present invention, the concentration of the cellulose nanofiber aqueous solution is preferably 0.5-2 wt%, specifically 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, or 2 wt%; the mass ratio of molybdenum disulfide to cellulose nanofiber in the aqueous solution is preferably 1:(2-8), specifically 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, or 1:8.

[0056] In the preparation steps of the MoS2-loaded cellulose nanofiber composite material provided by the present invention, the mixing is preferably carried out under stirring conditions; the mixing time is preferably 12-48h, specifically 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h or 48h; the ultrasonic temperature is preferably -5-5℃, specifically -5℃, -4℃, -3℃, -2℃, -1℃, 0℃, 1℃, 2℃, 3℃, 4℃ or 5℃; the ultrasonic time is preferably 5-20h, specifically 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h.

[0057] In the above-mentioned preparation steps of MoS2-loaded cellulose nanofiber composite material provided by the present invention, after the ultrasonic treatment is completed, centrifugation is performed to discard the precipitate and obtain the upper liquid containing the MoS2-loaded cellulose nanofiber composite material.

[0058] In the preparation method provided by the present invention, the mesoporous material loaded with bactericide is prepared according to the following steps:

[0059] The bactericide and mesoporous material are mixed in a liquid medium, and the liquid medium is removed to obtain a mesoporous material loaded with the bactericide.

[0060] In the preparation steps of the mesoporous material loaded with bactericide provided by the present invention, the mass ratio of the bactericide to the mesoporous material is preferably (1-10):1, specifically 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1; the liquid medium is preferably methanol; the amount ratio of the liquid medium to the mesoporous material is preferably (10-50) mL:0.1g, specifically 10mL:0.1g, 15mL:0.1g, 20mL:0.1g, 25mL:0.1g, 30mL:0.1g, 35mL:0.1g, 40mL:0.1g, 45mL:0.1g or 50mL:0.1g.

[0061] In the preparation steps of the mesoporous material loaded with bactericide provided by the present invention, the specific mixing process preferably includes: first dispersing the mesoporous material in a liquid medium and then evacuating it; then mixing in the bactericide; and then performing ultrasonic treatment and mechanical stirring in sequence; wherein the mechanical stirring is preferably carried out under closed conditions; the mechanical stirring time is preferably 12 to 48 hours, specifically 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours, 36 hours, 40 hours, 44 hours or 48 hours.

[0062] In the above-mentioned preparation steps of the mesoporous material loaded with bactericide provided by the present invention, the method of removing the liquid phase medium is preferably to repeatedly perform ethanol washing and filtration, and after the last filtration, the filtration product is dried to constant weight; the drying temperature is preferably 10-40℃, specifically 10℃, 15℃, 20℃, 25℃ (room temperature), 30℃, 35℃ or 40℃.

[0063] In the preparation method provided by this invention, the specific process of mixing polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-supported cellulose nanofiber composite material, mesoporous material loaded with bactericide, sulfuric acid, initiator and water preferably includes:

[0064] a) Mix polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-supported cellulose nanofiber composite material, sulfuric acid and water to obtain a mixture;

[0065] b) Mix the mesoporous material loaded with bactericide, the initiator and the mixture to obtain a hydrogel prepolymer.

[0066] In the mixing process provided by the present invention, step a) preferably includes the following specific mixing process:

[0067] a1) Mix polyvinyl alcohol, a portion of the aqueous solution of MoS2-loaded cellulose nanofiber composite material, and water to obtain a mixed liquid semi-finished product;

[0068] a2) Mix methacrylic acid betaine sulfonate, sulfuric acid solution and the remaining MoS2-loaded cellulose nanofiber composite aqueous solution, and then mix with the semi-finished mixture to obtain a mixture.

[0069] In the mixing process provided by the present invention, in step a1), the mixing temperature is preferably 85-99°C, specifically 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C or 95°C; the mixing time is preferably 1-5 hours, specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours.

[0070] In the mixing process provided by the present invention, in steps a1) and a2), the content of the MoS2-supported cellulose nanofiber composite material in the aqueous solution of the MoS2-supported cellulose nanofiber composite material is preferably 1 to 5 mg / mL, specifically 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL or 5 mg / mL.

[0071] In the mixing process provided by the present invention, in step a2), the concentration of the sulfuric acid solution is preferably 10-50 wt%, specifically 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%.

[0072] In the mixing process provided by the present invention, in step b), the mixture is preferably cooled to ambient temperature (room temperature) before being mixed.

[0073] In the preparation method provided by the present invention, the freezing temperature of the freeze-thaw treatment is preferably -30 to -50°C, specifically -30°C, -35°C, -40°C, -45°C, or -50°C; the freezing time (per cycle) of the freeze-thaw treatment is preferably 8 to 16 hours, specifically 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, or 16 hours; the thawing temperature of the freeze-thaw treatment is preferably 20 to 40°C, specifically 20°C, 25°C, 30°C, 35°C, or 40°C; the thawing time (per cycle) of the freeze-thaw treatment is preferably 8 to 16 hours, specifically 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, or 16 hours; the number of freeze-thaw cycles of the freeze-thaw treatment is preferably 1 to 5 times, specifically 1 time, 2 times, 3 times, 4 times, or 5 times.

[0074] The technical solution provided by this invention significantly improves the anti-adhesion, bactericidal, and mechanical properties of hydrogels by introducing mesoporous materials loaded with bactericides and MoS2-loaded cellulose nanofiber composites into the hydrogel. This technical solution, by constructing a hydrogel system of "anti-adhesion-bactericidal-enhanced mechanical properties," solves the problems of the single antifouling mechanism and poor mechanical properties of traditional hydrogels, providing a good solution for long-term antifouling of marine equipment.

[0075] For clarity, the following examples and comparative models will be used to provide a detailed description.

[0076] Example 1

[0077] (1) Synthesis of MoS2-supported cellulose nanofiber composite material (MoS2@CNF, MC):

[0078] MoS2@CNF was synthesized by exfoliating bulk molybdenum disulfide (MoS2) from an aqueous solution of cellulose nanofibers (CNF) using an ultrasonic method. The specific process included: adding 0.25 g of molybdenum disulfide to 100 mL of an aqueous solution of cellulose nanofibers (1 wt%), stirring continuously for 24 h, and then sonicating in an ice bath for 10 h; subsequently, centrifuging the solution at 4000 rpm for 10 min to remove the unexfoliated molybdenum disulfide (MoS2), and collecting the supernatant containing MoS2@CNF (MoS2@CNF content was 2 mg / mL).

[0079] The morphology of MoS2@CNF prepared in this embodiment was observed by TEM and the elemental distribution of Mo and S was analyzed. The results are as follows: Figure 1 As shown, Figure 1 These are TEM images of MoS2@CNF and EDS mapping images of Mo and S elements provided in Example 1 of this invention. Microstructural characterization by transmission electron microscopy (TEM) shows that the lateral dimensions of the MoS2@CNF nanosheets are mainly between 60 and 300 nm. The elemental mapping further confirms the presence of Mo and S substances distributed on the surface of the nanosheets, verifying the successful synthesis of MoS2@CNF.

[0080] (2) Preparation of mesoporous silica (ST) supported on brominated pyrrolidone:

[0081] 0.1 g of mesoporous silica was ultrasonically dispersed in 30 mL of anhydrous methanol, and the air in the pores was removed by vacuum. Then, 0.5 g of bromopyrrolidone was added to the above solution, ultrasonically dissolved, and then sealed and stirred continuously for 24 hours. After stirring, the product was washed with anhydrous ethanol and filtered three times. The product was dried at room temperature to constant weight.

[0082] (3) Preparation of high-toughness antifouling and antibacterial hydrogel:

[0083] 1.2g of polyvinyl alcohol (PVA, type 1799), 2.1g of the above-mentioned upper layer containing MoS2@CNF, and 4.2g of deionized water were mixed and stirred vigorously at 95°C for 3 hours to obtain mixture A; then, 0.6g of betaine methacrylate sulfonate (SBMA) and 2.4g of... A mixture of 30 wt% H2SO4 solution and 1.5 g of the above-mentioned upper layer containing MoS2@CNF was added to mixture A and stirred rapidly to obtain mixture B. After cooling mixture B to room temperature, 0.18 g of the above-mentioned mesoporous silica loaded with brominated pyrrolidone was added, and the mixture was stirred evenly. Then, 0.006 g of potassium persulfate (KPS) was added, and the mixture was centrifuged to remove air bubbles to obtain a hydrogel prepolymer. The mixed hydrogel prepolymer was poured into a mold, and the mold was frozen at -40°C and thawed at 30°C. The freeze-thaw cycle was repeated twice, with each cycle lasting 12 hours, to obtain a high-toughness antifouling and antibacterial hydrogel, denoted as PPSM4 (4 refers to the fact that MC accounts for 0.4 wt% of the total mass of PVP and PSBMA in the hydrogel).

[0084] Example 2

[0085] Referring to Example 1, the only difference is that the total amount of the upper liquid containing MoS2@CNF used in the hydrogel preparation process is 0.9g, and the resulting high-toughness antifouling and antibacterial hydrogel is designated as PPSM1.

[0086] Example 3

[0087] Referring to Example 1, the only difference is that the total amount of the upper liquid containing MoS2@CNF used in the hydrogel preparation process is 1.8g, and the resulting high-toughness antifouling and antibacterial hydrogel is denoted as PPSM2.

[0088] Example 4

[0089] Referring to Example 1, the only difference is that the total amount of the upper liquid containing MoS2@CNF used in the hydrogel preparation process is 5.4g, and the resulting high-toughness antifouling and antibacterial hydrogel is designated as PPSM6.

[0090] Example 5

[0091] Referring to Example 1, the only difference is that the total amount of the upper liquid containing MoS2@CNF used in the hydrogel preparation process is 7.2g, and the resulting high-toughness antifouling and antibacterial hydrogel is designated as PPSM8.

[0092] Comparative Example 1

[0093] Preparation of PVA hydrogel:

[0094] Add 1.2g of polyvinyl alcohol (PVA, type 1799) to 10.8g of deionized water, stir vigorously at 95℃ for 3 hours, cool to room temperature, add 0.006g of potassium persulfate (KPS), stir evenly, centrifuge to remove air bubbles, then pour the solution into a mold, and finally freeze the mold at -40℃ and thaw at 30℃, repeat the freeze-thaw cycle twice, with each cycle lasting 12 hours, to obtain PVA hydrogel.

[0095] Comparative Example 2

[0096] Preparation of PVA / PSBMA hydrogel:

[0097] First, PVA was dissolved in deionized water and stirred vigorously at 95°C for 3 hours to prepare a 16wt% PVA solution. Then, 0.6g of betaine methacrylate sulfonate (SBMA), 2.4g of H2SO4 solution (30wt%) and 1.5g of deionized water were mixed and added to 7.5g of the above PVA solution and stirred rapidly. The mixture was cooled to room temperature, 0.006g of potassium persulfate (KPS) was added, and the mixture was stirred evenly. The air bubbles were removed by centrifugation, and the solution was then poured into a mold. Finally, the mold was frozen at -40°C and thawed at 30°C, and the freeze-thaw cycle was repeated twice. The freezing and thawing time for each cycle was 12 hours to obtain a PVA / PSBMA hydrogel, denoted as PP.

[0098] Comparative Example 3

[0099] Referring to Example 1, the only difference is that mesoporous silica loaded with brominated pyrrolidone is not added during the hydrogel preparation process, and the resulting hydrogel is denoted as PPM.

[0100] Example 6

[0101] (1) Mechanical performance evaluation

[0102] The hydrogels prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to mechanical property tests. The tensile properties of the hydrogels at room temperature were tested using a tensile testing machine (GP-6113A, Gaopin Testing Instruments Co., Ltd.). Dumbbell specimens (20mm × 4mm × 2mm) were used for the tensile tests at a tensile rate of 10mm·min⁻¹. -1 Toughness was calculated by integrating the area under the stress-strain curve; the compressive strength of the hydrogel was tested using a computer-controlled electronic universal testing machine, with cylindrical hydrogel samples (20 mm in diameter and 10 mm in height) subjected to compression tests at a compression rate of 10 mm / min. -1 Toughness is calculated by integrating the area under the stress-strain curve when the strain is compressed to 90%.

[0103] Test results are as follows Figures 2-7The above, Figure 2 This is a tensile strain-stress curve of the hydrogel provided in Embodiment 6 of the present invention. Figure 3 This is a tensile strength diagram of the hydrogel provided in Embodiment 6 of the present invention. Figure 4 This is a graph showing the tensile toughness values ​​of the hydrogel provided in Embodiment 6 of the present invention. Figure 5 This is a compression strain-stress curve of the hydrogel provided in Embodiment 6 of the present invention. Figure 6 This is a compressive strength diagram of the hydrogel provided in Embodiment 6 of the present invention. Figure 7 This is a diagram showing the compressive toughness values ​​of the hydrogel provided in Embodiment 6 of the present invention.

[0104] The test results show that the tensile strength and strain of the PVA / PSBMA double-layer hydrogel are only 2 MPa and 380%, respectively. When the ratio of PVA to SBMA to CNF is 1:0.1 wt%, the tensile strength and strain of the PVA / PSBMA-MC-ST hydrogel are 3.1 MPa and 677%, respectively. When the ratio of PVA to SBMA to CNF is 1:0.4 wt.%, the tensile strength and strain of the PVA / PSBMA-MC-ST hydrogel are 6.42 MPa and 738%, respectively. The PVA / PSBMA-MC-ST hydrogel exhibits the highest toughness at 2061 kJ / m when the ratio of PVA to SBMA to CNF is 1:0.4 wt.%. 3 When all hydrogels are compressed to 90% strain, the compressive stress of pure PVA hydrogel at 90% strain is only about 0.14 MPa in the stress-strain curve; with the introduction of nano-MoS2, the compressive strength at 90% strain reaches as high as 1.73 MPa, and the toughness reaches 17 kJ / m. 3 .

[0105] (2) Evaluation of anti-protein adhesion

[0106] Anti-protein adhesion experiment: First, the FITC-labeled BSA-FITC solution was diluted to 1 mg / mL with PBS (pH=7.4); then, the hydrogel samples prepared in Example 1, Comparative Example 1, and Comparative Example 3 were immersed in the solution and incubated in a constant temperature shaking incubator at 26°C and 120 rpm for 36 hours; finally, the adhesion of BSA to the surface of the hydrogel was photographed using a fluorescence microscope (DM5000B, LEICA Ltd.).

[0107] Results of anti-protein adhesion experiments are as follows Figures 8-9 As shown, Figure 8 This is a fluorescence microscope image of the anti-BSA adhesion experiment of the hydrogel provided in Example 6 of the present invention. Figure 9 This is a BSA coverage diagram of the hydrogel provided in Embodiment 6 of the present invention.

[0108] The experimental results show that the PVA sample exhibits strong fluorescence under a fluorescence microscope, indicating that FITC-labeled bovine serum albumin is adsorbed in large quantities. However, the PVA / PSBMA-MC and PVA / PSBMA-MC-ST hydrogels show virtually no fluorescence, indicating that bovine serum albumin hardly adheres to the hydrogel. This is because a water film forms on the surface of the hydrogel, thus preventing protein adhesion.

[0109] (3) Evaluation of anti-algae adhesion

[0110] Anti-algae adhesion experiment: The hydrogel samples prepared in Example 1, Comparative Example 1, and Comparative Example 3 were cut into certain sizes and placed together with Chlorella in f / 2 medium containing silica. They were cultured at a constant temperature of 23°C for one week. Then, the hydrogel samples were removed and placed under a biological microscope (E200MV, Nikon Ltd.) to observe the adhesion of Chlorella on the surface of the hydrogel. Finally, the coverage of the adhesion area was calculated using ImageJ software.

[0111] Results of anti-algae adhesion experiments are as follows Figures 10-11 As shown, Figure 10 This is an experimental diagram illustrating the anti-Chlorella adhesion of the hydrogel provided in Example 6 of the present invention. Figure 11 This is a diagram showing the Chlorella coverage of the hydrogel provided in Embodiment 6 of the present invention.

[0112] The experimental results show that after one week of cultivation in Chlorella suspension, PVA samples exhibit significant algal adhesion with a surface coverage of approximately 2.9%. In stark contrast, algal adhesion of PVA / PSBMA-MC and PVA / PSBMA-MC-ST hydrogels is negligible, confirming their superior anti-algal adhesion properties.

[0113] (4) Antibacterial evaluation

[0114] Antibacterial test: Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli were cultured separately in LB broth; the bacterial suspensions were centrifuged and then redispersed in physiological saline to 10⁻⁶ oz. 9 CFU·mL -1As the final bacterial suspension; the eight groups were: (I) control group, (II) MoS2 (from Example 1, the same below), (III) CNF (from Example 1, the same below), (IV) MoS2@CNF (from Example 1, the same below), (V) control group + near-infrared, (VI) MoS2 + near-infrared, (VII) CNF + near-infrared, (VIII) MoS2@CNF + near-infrared; then, 100 μL of bacterial suspension and 900 μL of bactericide dispersion were placed in a 1.5 mL centrifuge tube, mixed and sealed; then, near-infrared (808 nm, 1 W·cm) was applied. -2 Irradiate for 10 minutes; then, shake the centrifuge tubes on a high-speed stirrer for 60 seconds, and then place them in a constant temperature shaker (120 rpm, 37°C) for 10 minutes; drop 100 μL of the mixture onto the surface of the culture medium and spread it evenly with a triangular glass rod. Finally, place the culture medium in an incubator at 37°C and observe the growth of the surface colonies.

[0115] Antibacterial test results as follows Figures 12-13 As shown, Figure 12 These are optical photographs of the antibacterial properties of different materials (CNF, MoS2, MoS2@CNF) against Escherichia coli and Staphylococcus aureus under and without near-infrared light irradiation, provided in Embodiment 6 of the present invention. Figure 13 The inhibition rates of different materials (CNF, MoS2, MoS2@CNF) provided in Example 6 of this invention against Escherichia coli and Staphylococcus aureus under near-infrared light irradiation.

[0116] The experimental results show that, under conditions without near-infrared (NIR) irradiation, dense bacterial growth (Escherichia coli / Staphylococcus aureus) was observed in the control group, MoS2 group, and pure carrier (CNF) group. Compared with the control group, the number of colonies in the MoS2@CNF group was slightly lower, indicating that the CNF carrier effectively improved the dispersibility of MoS2 nanosheets and their contact efficiency with bacteria. However, after near-infrared laser irradiation of MoS2@CNF, the bacterial survival rate decreased significantly. The antibacterial efficiency of MoS2@CNF nanosheets against Escherichia coli and Staphylococcus aureus even exceeded 99.9%, confirming its excellent bactericidal ability under near-infrared irradiation.

[0117] (5) Actual marine antifouling performance evaluation

[0118] To further evaluate the actual antifouling effect, the hydrogel samples prepared in Example 1, Comparative Example 1, and Comparative Example 3 were subjected to a 90-day sea test in Haikou Bay. The average water temperature in this area was 25°C, the relative humidity was 84%, the shallow water salinity was 29.6-31.8%, and the nearshore seawater was rich in organic matter and inorganic salts.

[0119] Marine antifouling experiment results as follows Figures 14-15 As shown, Figure 14 These are real photos taken after the hydrogel provided in Embodiment 6 of the present invention underwent a 90-day sea test in Haikou Bay. Figure 15 This is a dirt coverage diagram of the hydrogel provided in Embodiment 6 of the present invention.

[0120] The experimental results show that the surface of the PVA hydrogel is almost completely scaled (coverage rate up to 97%), while the surface of the PVA / PSBMA-MC-ST hydrogel is very clean (coverage rate only 0.1%), demonstrating the superior antifouling performance of the PVA / PSBMA-MC-ST hydrogel.

[0121] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A high-toughness, antifouling, and antibacterial hydrogel, characterized in that, It is made by mixing polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-loaded cellulose nanofiber composite material, mesoporous material loaded with bactericide, sulfuric acid, initiator and water, and then subjecting it to freeze-thaw treatment.

2. The high-toughness antifouling and antibacterial hydrogel according to claim 1, characterized in that, The amount of the MoS2-supported cellulose nanofiber composite material is 0.05 to 1.5 wt% of the total mass of polyvinyl alcohol and betaine sulfonate methacrylate.

3. The high-toughness antifouling and antibacterial hydrogel according to claim 1, characterized in that, The bactericide in the mesoporous material loaded with bactericide is one or more of bromopyrrolidone, iodopyridinol, chitosan quaternary ammonium salt and benzisothiazolinone; the mesoporous material in the mesoporous material loaded with bactericide is mesoporous silica.

4. The high-toughness antifouling and antibacterial hydrogel according to claim 1, characterized in that, The amount of the mesoporous material loaded with the bactericide is 5 to 20 wt% of the total mass of polyvinyl alcohol and betaine sulfonate methacrylate.

5. The high-toughness antifouling and antibacterial hydrogel according to claim 1, characterized in that, The initiator is one or more of potassium persulfate, ammonium persulfate, and sodium persulfate.

6. The high-toughness antifouling and antibacterial hydrogel according to claim 1, characterized in that, The mass ratio of polyvinyl alcohol, betaine sulfonate methacrylate, sulfuric acid, and initiator is 1.2:(0.4-0.8):(0.5-1):(0.004-0.008).

7. A method for preparing the high-toughness antifouling and antibacterial hydrogel according to any one of claims 1 to 6, characterized in that, Includes the following steps: Polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-loaded cellulose nanofiber composite material, mesoporous material loaded with bactericide, sulfuric acid, initiator and water were mixed to obtain a hydrogel prepolymer solution. The hydrogel prepolymer solution was subjected to freeze-thaw treatment to obtain a high-toughness antifouling and antibacterial hydrogel.

8. The preparation method according to claim 7, characterized in that, The mixing process specifically includes: Polyvinyl alcohol, betaine methacrylate sulfonate, MoS2-supported cellulose nanofiber composite material, sulfuric acid and water were mixed to obtain a mixture. A mesoporous material loaded with a bactericide, an initiator, and the mixture are combined to obtain a hydrogel prepolymer.

9. The preparation method according to claim 7, characterized in that, The MoS2-supported cellulose nanofiber composite material was prepared according to the following steps: MoS2-loaded cellulose nanofiber composite material was obtained by mixing molybdenum disulfide with an aqueous solution of cellulose nanofibers and then subjecting the mixture to ultrasonic treatment.

10. The preparation method according to claim 7, characterized in that, The mesoporous material loaded with the bactericide is prepared according to the following steps: The bactericide and mesoporous material are mixed in a liquid medium, and the liquid medium is removed to obtain a mesoporous material loaded with the bactericide.

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