A double bond-terminated cationic silicone waterborne polyurethane and a method for preparing the same, and an antifog sterilized hydrogel, an antifog sterilized coating

Abstract

This invention discloses a double-bond-terminated cationic organosilicon waterborne polyurethane, its preparation method, and an anti-fogging and sterilizing hydrogel and coating, belonging to the field of medical materials technology. A double-bond-terminated cationic organosilicon waterborne polyurethane is obtained by reacting triethylene glycol, 3-dimethylamino-1,2-propanediol, hydroxypropyl silicone oil, isophorone diisocyanate, chain extender bis(2-hydroxyethyl) disulfide, and end-capping agent hydroxyethyl methacrylate. A hydrophilic-hydrophobic heteropolymer network is constructed, achieving rapid water spreading and anti-swelling properties. It possesses contact-active antibacterial and self-cleaning properties and forms a stable Si-O-Si covalent interface to achieve excellent substrate adhesion. The prepared coating shows broad application prospects in the functionalization of optical device surfaces, laying a reliable material foundation for the development of safer and more durable medical optical components.

Description

Technical Field

[0001] This invention belongs to the field of medical materials technology, specifically relating to a double-bond-terminated cationic organosilicon waterborne polyurethane and its preparation method, as well as an anti-fogging sterilization hydrogel and an anti-fogging sterilization coating. Background Technology

[0002] In everyday use, fogging of eyeglass lenses reduces visual comfort and affects travel safety. In clinical settings, fogging on ophthalmic endoscopes and surgical microscopes can obstruct the surgical field, prolong surgery time, and even increase the risk of intraoperative injury. Furthermore, the inherent temperature, humidity, and nutrient supply characteristics of the ocular surface microenvironment promote microbial colonization and biofilm formation. Traditional antibacterial coatings typically rely on the continuous release of biocides to achieve their antibacterial effect, but such designs may irritate corneal or conjunctival tissues and disrupt tear film homeostasis. Therefore, there is an urgent need to develop multifunctional coatings that combine long-lasting anti-fogging performance, strong antibacterial activity, and good biocompatibility.

[0003] Existing passive anti-fogging technologies are mainly divided into two categories: superhydrophobic coatings and superhydrophilic coatings. Superhydrophobic coatings, with their low surface energy, repel water and can remove water droplets larger than approximately 10 micrometers in diameter through gravity-driven rolling. However, in the early condensation stage before the droplets reach this size, these coatings inevitably accumulate fog. Furthermore, these coatings fail when nanoscale condensate penetrates into the Cassie-Baxter state. In contrast, superhydrophilic coatings promote rapid water droplet diffusion to form a continuous film, but they have two inherent drawbacks: water absorption leads to volume expansion, reducing optical transparency; and repeated drying-expansion cycles cause decreased mechanical stability, leading to wrinkles and delamination. To overcome these limitations, "hydrophilic / hydrophobic heterogeneous networks" (also known as "dual-wetting" materials) have become a key strategy to overcome the bottleneck of single wetting mechanisms.

[0004] In 2022, Shi et al. developed a long-lasting anti-fogging coating with strong interfacial adhesion and a heterogeneous network structure. This coating can be reused over a wide temperature range and effectively avoids wrinkles caused by interfacial failure and expansion (Advanced Science, 2022, 9, 14, 2200072). In 2024, Liu et al. constructed a composite network using silane coupling agents (A151, KH570) and hydrophilic monomers, significantly improving adhesion and anti-fogging durability (Progress in Organic Coatings, 2024, 196, 108690). Despite these advancements, such coatings still primarily focus on the single function of anti-fogging and cannot meet the comprehensive needs of multifunctional surfaces that combine anti-fogging and sterilization in practical applications. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] One objective of this invention is to provide a double-bond-terminated cationic organosilicon waterborne polyurethane, the structural formula of which is as follows. , Where n is a positive integer and n≥1.

[0008] Another object of the present invention is to provide a method for preparing the double-bond-terminated cationic organosilicon waterborne polyurethane as described above, which is obtained by reacting triethylene glycol, 3-dimethylamino-1,2-propanediol, hydroxypropyl silicone oil, isophorone diisocyanate, chain extender bis(2-hydroxyethyl) disulfide, and end-capping agent hydroxyethyl methacrylate in a molar ratio of 35-36:32-33:1:100:13-14:36-37.

[0009] As a preferred embodiment of the preparation method of the double-bond-terminated cationic organosilicon aqueous polyurethane of the present invention, the reaction specifically comprises: Isophorone diisocyanate, hydroxypropyl silicone oil, tetraethylene glycol, and 3-dimethylamino-1,2-propanediol were reacted under nitrogen protection in the presence of a catalyst and a viscosity modifier to prepare terminal isocyanate prepolymers. After adding the chain extender bis(2-hydroxyethyl) disulfide to the isocyanate prepolymer and reacting it, the end-capping agent hydroxyethyl methacrylate is added and reacted.

[0010] In a preferred embodiment of the preparation method of the double-bond-terminated cationic organosilicon waterborne polyurethane of the present invention, the catalyst comprises one or more of dibutyltin di(dodecanoate), bismuth neodecanoate, stannous octoate, triethylenediamine, and zirconium isooctanoate; the amount of catalyst added is 0.5-2% of the total mass of isophorone diisocyanate, hydroxypropyl silicone oil, tetraethylene glycol, and 3-dimethylamino-1,2-propanediol. The viscosity modifier includes one or more of acetone, methyl acrylate, methyl methacrylate, ethyl lactate, 2-methyltetrahydrofuran, butanone, and cyclohexanone; the amount of the viscosity modifier added is 50-90% of the total mass of isophorone diisocyanate, hydroxypropyl silicone oil, tetraethylene glycol and 3-dimethylamino-1,2-propanediol.

[0011] As a preferred embodiment of the preparation method of the double-bond-terminated cationic organosilicon waterborne polyurethane of the present invention, wherein: the reaction is carried out under nitrogen protection, the reaction temperature is 70~90 ℃, and the reaction time is 2~5 h; The reaction involving the addition of the chain extender bis(2-hydroxyethyl) disulfide is carried out at a temperature of 60-80°C and a reaction time of 0.5-2 hours. The reaction involving the addition of the capping agent hydroxyethyl methacrylate takes place at a temperature of 60-80°C for 0.5-2 hours.

[0012] Another object of the present invention is to provide a method for preparing an anti-fogging and sterilizing hydrogel, comprising, Acrylamide and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide were dissolved in a solvent, and hydroxyethyl methacrylate, sodium polystyrene sulfonate, silane coupling agent and the double-bond-terminated cationic organosilicon waterborne polyurethane as described in claim 1 were added in sequence. 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, an ultraviolet photoinitiator, was added, and the mixture was uniformly dispersed in the dark.

[0013] As a preferred embodiment of the preparation method of the anti-fogging and sterilizing hydrogel of the present invention, the hydrogel comprises, by weight, 0.5 to 3 parts of hydroxyethyl methacrylate, 0.5 to 3 parts of acrylamide, 0.1 to 1 part of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide, 0.01 to 0.5 parts of sodium polystyrene sulfonate, 0 to 0.2 parts of silane coupling agent, 0.1 to 10 parts of double-bond-terminated cationic organosilicon waterborne polyurethane, and 0.1 to 3 parts of ultraviolet photoinitiator.

[0014] In a preferred embodiment of the preparation method of the anti-fogging and sterilizing hydrogel of the present invention, the silane coupling agent includes one or two of 3-(trimethoxysilyl)methacrylate (KH-570) and acryloyloxypropyltrimethoxysilane. The ultraviolet photoinitiator includes one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-2-methyl-1-phenylacetone, lithium phenyl(2,4,6-trimethylbenzoyl)phosphonate, and 1-hydroxycyclohexylphenyl ketone; The solvent is one or both of water and bacterial cellulose dispersant.

[0015] Another object of the present invention is to provide an anti-fogging and sterilizing hydrogel obtained by the preparation method described above.

[0016] Another objective of this invention is to provide an anti-fog sterilization coating, which is obtained by uniformly coating the anti-fog sterilization hydrogel as described above onto a substrate and curing it under ultraviolet light.

[0017] Based on a hydrophilic hydrogel network, a strongly hydrated surface is constructed through component regulation, mimicking the physical anti-adhesion function of a mucopolysaccharide layer. Utilizing the zwitterionic structure of SBMA and the hydrophilic groups of PSS, a dense hydrophilic interface is formed, significantly inhibiting initial bacterial colonization. Furthermore, the double-bond-terminated cationic organosilicon waterborne polyurethane (WSPU) in the coating, along with the positively charged amino groups carried by SBMA, mimics the chemical attack role of antimicrobial peptides in fish mucus. Through electrostatic interactions, it precisely targets the negatively charged bacterial cell membrane, and by inserting its hydrophobic alkyl chains, it disrupts the integrity of the membrane lipid bilayer, effectively killing already attached bacteria. This preparation process requires no additional chemical bactericides, avoiding the risk of ocular irritation. The room-temperature light curing process achieves good compatibility with the hydrogel system, ensuring synergistic effects of antibacterial self-cleaning and anti-fogging properties, meeting the comprehensive needs of medical materials for multifunctional surfaces with anti-fogging and sterilization capabilities.

[0018] As a preferred embodiment of the anti-fogging and sterilizing coating of the present invention, the following steps are performed: the substrate is ultrasonically cleaned sequentially in acetone, anhydrous ethanol, and deionized water to thoroughly remove surface contaminants, followed by drying; the substrate is then subjected to air plasma treatment to activate the surface and introduce hydroxyl groups (-OH), thereby improving hydrophilicity and coating adhesion; next, an anti-fogging and sterilizing hydrogel solution is applied to the pretreated substrate using a wire bar coater to obtain a uniform liquid film; the coated substrate is immediately placed in an ultraviolet curing chamber for ultraviolet irradiation (365 nm wavelength, 0.8 Wcm²). -2 After 1 hour, the final coating is obtained.

[0019] Compared with the prior art, the present invention has the following beneficial effects: This invention proposes a hierarchical bonding network strategy, breaking through the traditional "single-component enhancement" method, and develops a multifunctional cationic biomimetic hydrogel coating that successfully integrates anti-fogging, anti-swelling, antibacterial, self-cleaning, strong adhesion, and excellent biocompatibility properties into a single material system. This hierarchical bonding paradigm overcomes the key trade-offs between these functions, providing a new method for surface functionalization of surgical optical devices, and is expected to improve their safety and efficiency. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein: Figure 1 This is a synthetic route diagram for the double-bond-terminated cationic organosilicon waterborne polyurethane (WSPU) of the present invention. Figure 2The average particle size of the 15 wt% WSPU dispersion obtained in Example 1 of this invention is ( Figure 2 a) and Zeta potential ( Figure 2 (b) Figure 3 The hydrogen nuclear magnetic resonance spectrum of the WSPU obtained in Example 1 of this invention; Figure 4 This is a Fourier transform infrared (FTIR) spectrum analysis diagram of the WSPU obtained in Example 1 of the present invention. Detailed Implementation

[0021] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0022] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0023] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0024] Unless otherwise specified, all raw materials used in the examples are commercially available.

[0025] Example 1

[0026] This embodiment provides a method for preparing a 15 wt% aqueous polyurethane dispersion, the synthesis route of which is as follows: Figure 1 As shown, it includes the following steps: First, tetraethylene glycol triethylene glycol (TEG) and 3-dimethylamino-1,2-propanediol (DMAPD) ​​were dehydrated at 120°C for 6 hours and then cooled for later use. Hydroxypropyl silicone oil (TOEA) was dehydrated under vacuum at less than 0.1 MPa for 6 hours and then cooled for later use. Isophorone diisocyanate (IPDI) was dried over a 3 Å molecular sieve for one week for later use. During the synthesis, isophorone diisocyanate (6.16 g, 27.70 mmol), hydroxypropyl silicone oil (0.60 g, 0.275 mmol), tetraethylene glycol (1.89 g, 9.72 mmol), 3-dimethylamino-1,2-propanediol (1.07 g, 9.00 mmol), 0.1 g of catalyst dibutyldistin(dodecaenoic acid) (DBTDL), and 30 g of viscosity modifier acetone were placed in a four-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser, and nitrogen inlet and outlet. NCO prepolymer was prepared by reacting at 80°C for 3 h under nitrogen protection. The system was then cooled to 70°C, and bis(2-hydroxyethyl) disulfide (HED, 0.57 g, 3.70 mmol) was added as a chain extender and reacted for 1 h. A solution of hydroxyethyl methacrylate (HEMA, 1.30 g, 10.01 mmol) in acetone was then added as a capping agent, and the reaction continued for another 1 h. The temperature was then lowered to 60°C, and acetic acid (HAc, 0.54 g, 9.00 mmol) was added for neutralization for 2 h. Upon completion of the reaction, Fourier transform infrared spectroscopy (FTIR) was used to monitor the reaction up to 2270 cm⁻¹. -1 The isocyanate characteristic absorption peak completely disappeared to confirm the reaction endpoint. Finally, the product was dispersed in deionized water at 2000 rpm for 1 h, and then acetone was removed by rotary evaporation to obtain a WSPU dispersion with a solid content of 15 wt%.

[0027] The average particle size of the aqueous polyurethane dispersion is as follows: Figure 2 As shown in a, the Zeta potential of the aqueous polyurethane dispersion is as follows: Figure 2 As shown in b in the figure, the average particle size of the resulting dispersion is approximately 88.9 nm, and the Zeta potential is stable with an absolute value greater than 30 mV, indicating that the dispersion system possesses excellent colloidal stability.

[0028] use 1 The chemical structure of the WSPU was characterized by 1H NMR (500 MHz, CDCl3), and the results are as follows: Figure 3As shown, characteristic proton signals at δ 6.1 and 5.6 ppm, belonging to the HEMA terminal double bond (-C(CH3)=CH2), confirm the successful introduction of polymerizable double bonds; the sharp single peak near δ 0.1 ppm corresponds to the proton resonance of Si-CH3 in hydroxypropyl silicone oil, indicating that the organosilicon segment has been incorporated into the polymer backbone; the broad peak at δ 3.0 ppm belongs to the quaternary ammonium salt group (-N... + The presence of a methyl proton in (CH3)2 confirms the successful construction of the cation center. Furthermore, the observation of a methylene proton signal adjacent to the disulfide bond (-SS-) near δ 2.8 ppm verifies the introduction of a dynamic disulfide bond extender. The simultaneous presence of these characteristic peaks, combined with the fact that the integral ratios of each peak are in good agreement with the theoretical feed ratio, confirms the successful preparation of the target product WSPU.

[0029] Fourier transform infrared (FTIR) spectroscopy analysis of WSPU as follows Figure 4 As shown, WSPU exhibits characteristic spectral bands. Specifically, in the range of 2947–2902 cm⁻¹. -1 The bands observed at 3330 cm⁻¹ are attributed to the presence of -CH₂ and -CH₃ groups. -1 and 1536cm -1 The bands at 1243 cm⁻¹ correspond to the stretching and bending vibrations of the NH group in the carbamate bond, respectively. -1 The peak is attributed to the CN stretching vibration of the amide group. 1705 cm⁻¹ -1 The appearance of a band at 1642 cm⁻¹ indicates the C=O stretching vibration, confirming the presence of the -NHCOO- structure in the synthesized polymer. -1 The band at 1258 cm⁻¹ is attributed to the C=C stretching vibration, indicating that HEMA (hydroxyethyl methacrylate) has been successfully incorporated into the polymer chain. -1 The sharp absorption peak at 802 cm⁻¹ is attributed to the symmetric bending vibration of Si-CH₃, which partially overlaps with the CN stretching vibration of WSPU. -1 The absorption peak at 1097-1028 cm⁻¹ is attributed to the in-plane rocking vibration of Si-CH₃, indicating the presence of abundant Si(CH₃)₂ groups in the system. -1 The strong absorption bands appearing within this range correspond to the characteristic absorption region of the Si-O-Si bonds in the main chain. In short-chain compounds, Si-O-Si absorption bands occur in the range of 1020–1085 cm⁻¹. -1 The spectrum initially exhibits a single band; however, as the chain length increases, this band splits into two absorption peaks of similar intensity, a key characteristic of polysiloxanes. Aliphatic polyethers such as TEG (tetraethylene triethylene glycol) exhibit similar absorption peaks in the 1150–1060 cm⁻¹ range due to the presence of COC bonds. -1A broad and strong absorption peak is observed within this range, which partially overlaps with the characteristic bands of Si-O-Si. All these characteristics indicate that the organosilicon segment has been successfully incorporated into the polyurethane backbone. Furthermore, at 2270 cm⁻¹... -1 The characteristic band of the -NCO group was not observed at 3590 cm⁻¹ because NCO reacts with the active hydrogen of the hydroxyl-containing compound to form a carbamate bond. -1 The absence of a distinct absorption peak indicates that the hydroxyl group has largely participated in the reaction. The above discussion confirms the successful functionalization of the monomer.

[0030] Example 2

[0031] This embodiment provides a method for preparing an anti-fogging and sterilizing hydrogel coating, comprising the following steps: In a 250 mL beaker, acrylamide (AM, 1.0 g) and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide (SBMA, 0.295 g) were added sequentially, followed by bacterial cellulose dispersant (BC, 0.8% by mass, purchased from Guilin Qihong Technology Co., Ltd., 1.449 g), and stirred until dissolved. Subsequently, hydroxyethyl methacrylate (HEMA, 1.0 g), sodium polystyrene sulfonate (PSS, 0.1 g), silane coupling agent KH-570 (0.02 g), and double-bond-terminated cationic organosilicon waterborne polyurethane (WSPU, 0.48 g) were added sequentially to the same beaker, and stirred continuously at room temperature until all components were completely dissolved to form a homogeneous solution. Finally, the UV photoinitiator 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone (Irgacure 2959, 0.12 g) was added, and the mixture was stirred in the dark for 20 min to disperse it evenly into a hydrogel.

[0032] A glass substrate (25 mm × 76 mm × 1 mm) was sequentially ultrasonically cleaned for 15 min each in acetone, anhydrous ethanol, and deionized water to thoroughly remove surface contaminants, followed by drying in a 60°C oven. The substrate was then subjected to air plasma treatment (150 W, 3 min) to activate the surface and introduce hydroxyl groups (-OH), thereby improving hydrophilicity and coating adhesion. Next, a wire-bar coater was used to apply the sample solution onto the pretreated substrate, obtaining a uniform liquid film with a thickness of 200 μm. Finally, the coated substrate was immediately placed in a UV curing chamber for UV irradiation (365 nm wavelength, 0.8 W / cm²). -2 After 1 hour, the final anti-fog sterilization coating AFH-1 is obtained.

[0033] Example 3

[0034] This embodiment provides a method for preparing an anti-fogging and sterilizing hydrogel coating. The difference between this method and Example 2 is that the amount of double-bond-terminated cationic silicone waterborne polyurethane (WSPU) added is 0.64 g, and the amount of bacterial cellulose dispersant added is 1.529 g. The types and amounts of other components, experimental steps, and reaction times are the same as in Example 2. An anti-fogging and sterilizing coating AFH-2 is obtained.

[0035] Example 4

[0036] This embodiment provides a method for preparing an anti-fogging and sterilizing hydrogel coating. The difference between this method and Example 2 is that the amount of double-bond-terminated cationic silicone waterborne polyurethane (WSPU) added is 0.80 g, and the amount of bacterial cellulose dispersant added is 1.61 g. The types and amounts of other components, experimental steps, and reaction times are the same as in Example 2. An anti-fogging and sterilizing coating AFH-3 is obtained.

[0037] Comparative Example 1

[0038] This comparative example provides a method for preparing a hydrogel coating. The difference between this method and Example 2 is that the silane coupling agent, WSPU, and bacterial cellulose dispersant are no longer added; instead, 1.197 g of water is added to replace the bacterial cellulose dispersant as a solvent. The types and amounts of other components, experimental procedures, and reaction times are the same as in Example 2. The hydrogel coating AFH-4 is obtained.

[0039] Comparative Example 2

[0040] This comparative example provides a method for preparing a sterile hydrogel coating. The difference between this method and Example 2 is that the silane coupling agent and WSPU are no longer added, and the amount of bacterial cellulose dispersant used is 1.197 g. The types and amounts of other components, experimental steps, and reaction times are the same as in Example 2. A sterile hydrogel coating AFH-5 is obtained.

[0041] Comparative Example 3

[0042] This comparative example provides a method for preparing a sterile hydrogel coating. The difference from Example 2 is that WSPU is no longer added, and the amount of bacterial cellulose dispersant used is 1.207 g. The types and amounts of other components, experimental steps, and reaction times are the same as in Example 2. A sterile hydrogel coating AFH-6 is obtained.

[0043] The performance of the coating materials of Examples 2-4 and Comparative Examples 1-3 was tested using the following methods: (1) Anti-fogging performance test: Anti-fogging performance was distinguished by a hot steam test. Specifically, the sample was placed above a constant temperature water bath, with a distance of 5 cm between the sample and the water surface. It was then moved and photographed immediately under normal temperature conditions. In the fogging test, the light transmittance in the wavelength range of 400-800 nm was collected using a UV-Vis spectrophotometer. For comprehensive evaluation and direct comparison, the average transmittance T% in the wavelength range of 400-800 nm was defined and obtained by the following formula: , Where T(x) is the light transmittance at wavelength x nm.

[0044] (2) Water absorption and volume swelling performance test: The hydrogel sample was made into a disc shape (diameter d = 12 mm, height h = 5 mm), dried at 70℃ to constant weight, and then immersed in deionized water. The sample was taken out at intervals, the surface moisture was wiped off and weighed until the mass no longer changed. The water uptake ratio (WUR) of the hydrogel sample was calculated by the mass change of the hydrogel sample before and after water absorption. The calculation formula is as follows: , Among them, w0 and w t These represent the mass of the hydrogel sample before and after absorbing water for a period of time.

[0045] The volume swelling ratio (VSR) of a hydrogel sample (diameter d = 12 mm, height h = 5 mm) is calculated by measuring the change in the diameter of the disc before and after swelling. The formula is as follows: , Where d0 and d t These represent the diameters of the hydrogel samples before and after swelling, respectively. h0 and h... t These are the heights of the hydrogel samples before and after swelling for a period of time, respectively.

[0046] (3) Overlap Shear Adhesion Test: The adhesive strength of the six networks in Examples 2-4 and Comparative Examples 1-3 was tested by shear overlap tests on two substrates of two materials (i.e., glass and PMMA). For the adhesion test, the sample was applied to one end of the adhesive. This end was then covered by an adhesive end with an overlap shear configuration of 25 mm × 25 mm. The adhesives were pressed together and stored in water at room temperature for 5 days before testing. The overlap shear adhesion test was performed on an Instron 3365 testing machine equipped with a 5 kN load cell. The attachment was pulled apart at a speed of 5 mm / min until breakage occurred. The adhesive strength was calculated by dividing the force at breakage by the weight area.

[0047] (4) Antibacterial test: The antibacterial properties of the coating were assessed by plate counting of Gram-negative Escherichia coli (CMCC 44102, E. coli) and Gram-positive Staphylococcus aureus (CMCC 26003, S. aureus). Both E. coli and S. aureus were cultured in LB medium (containing 1% w / v NaCl, 0.5% w / v yeast extract, and 1% w / v tryptone). First, the bare and coated glass substrates (1×1 cm²) were subjected to ultraviolet radiation. 2 Sterilize. Then, immerse it in 1000 μL of bacterial suspension (2 × 10⁻⁶) in a 12-well microplate. 6 The bacterial suspension was incubated at 37°C with shaking for 4 hours (CFU / mL) to promote bacterial growth. After dilution, 20 μL of the diluted solution was spread onto LB nutrient agar plates and incubated at 37°C for 24 hours. Finally, the colony count was calculated using the following formula to determine the antibacterial rate (G%) of both bare and coated glass substrates.

[0048] , Wherein, N0 is the number of colonies after incubation on the bare glass substrate (without coating), and N1 is the number of colonies after incubation on the sterile hydrogel-coated glass substrate.

[0049] The performance test results of the coating materials in Examples 2-4 and Comparative Examples 1-3 are shown in Table 1.

[0050] Table 1

[0051] As shown in Table 1, the anti-fogging and sterilization coatings prepared in Examples 2-4 exhibit excellent effects. Compared to Example 4, Comparative Example 1 did not add silane coupling agent, waterborne polyurethane, or bacterial cellulose dispersant, resulting in decreased coating density and a significantly increased water absorption and swelling rate, affecting the long-term anti-fogging performance of the coating. Compared to Example 4, Comparative Example 2 did not add silane coupling agent or waterborne polyurethane, resulting in insufficient interfacial bonding strength and decreased adhesion performance. Compared to Example 4, Comparative Example 3 did not add waterborne polyurethane, resulting in a lack of hydrophobic microregions and ionic crosslinking networks in the coating, and a reduced wet modulus, affecting the coating's anti-swelling and cycling stability. The AFH-3 sample prepared in Example 4 integrates high optical transparency, excellent anti-fogging performance, low volume expansion rate, excellent biocompatibility, and strong interfacial adhesion in the same system. It also possesses stable wet-dry cycling performance, highly efficient antibacterial effect, and can achieve strong bonding with various transparent substrates through a unique hybrid failure mode.

[0052] Example 5

[0053] This embodiment provides a method for preparing an anti-fogging and sterilizing hydrogel coating. The difference between this method and Comparative Example 3 is that the amount of double-bond-terminated cationic organosilicon waterborne polyurethane (WSPU) added is adjusted to 0.32g, 0.48g, 0.64g, 0.80g, and 0.96g, respectively. The types and amounts of other components, experimental steps, and reaction times are the same as those in Comparative Example 3.

[0054] The anti-fogging time test method was as follows: the anti-fogging performance of the coating was evaluated using the hot steam exposure method. The sample was placed 5 cm above the surface of a constant-temperature water bath, and timing was started from the time the sample was placed until fogging or surface wrinkling and swelling occurred. The anti-fogging test was conducted at a water bath temperature of 80 ℃. The test results are shown in Table 2.

[0055] Table 2

[0056] Experimental results show that the optimal addition amount of WSPU is 0.48~0.80g. When the amount is less than 0.48g, the quaternary ammonium salt density in the coating is insufficient, the antibacterial activity is significantly reduced, and the network crosslinking density is insufficient, resulting in a decrease in antifogging durability. When the amount is greater than 0.80g, excessive ionic crosslinking occurs with sodium polystyrene sulfonate (PSS), leading to emulsion demulsification, precipitation, and the inability to form a uniform coating.

[0057] Example 6

[0058] This embodiment provides a method for preparing an anti-fogging and sterilizing hydrogel coating. The difference between this method and Example 2 is that the amount of silane coupling agent (KH-570) added is adjusted to 0.01g, 0.02g, and 0.03g, respectively. The types and amounts of other components, experimental steps, and reaction times are the same as in Example 2.

[0059] The mechanical properties of each coating were measured at room temperature using a computer-controlled universal testing machine (FL4503). Each sample was tested five times, and the results are expressed as averages.

[0060] (1) In the tensile test, dumbbell-shaped specimens with dimensions of 50 mm × 4 mm × 2 mm were prepared, with a preload of 0 N and a crosshead speed of 10 mm / min. For the compression test, cylindrical specimens with a diameter of 12 mm and a height of 5 mm were used, with a preload of 0 N and a compression rate of 3 mm / min. The single-cycle compressive strain was set to 96%, and the 10-cycle compressive strain was set to 80%.

[0061] (2) Peel Adhesion Test: Peel adhesion strength was measured according to ASTM D4541-22 using a digital semi-automatic peel tester (BGD500) equipped with a 16 mm diameter aluminum slider. Before testing, the aluminum slider was bonded to the coating surface using a two-component epoxy adhesive and cured at 25 °C for 24 h. During the test, the pressure was approximately 1 MPa·min⁻¹. -1 A tensile load perpendicular to the surface is applied at a rate until failure occurs at the coating / substrate interface. The peel strength is recorded directly by the instrument.

[0062] The test results are shown in Table 3.

[0063] Table 3

[0064] Experimental results show that the optimal addition amount of silane coupling agent (KH-570) is 0.02g. If the addition amount is too low, the interfacial anchoring effect is insufficient, the adhesion strength between the coating and the substrate decreases significantly, and peeling is likely to occur. If the addition amount is too high, the Si-O-Si inorganic network in the system undergoes excessive cross-linking, resulting in excessive rigidity and increased brittleness of the coating, making it prone to microcracks under swelling or external force.

[0065] Example 7

[0066] This embodiment provides a method for preparing an anti-fogging and sterilizing hydrogel coating. The difference between this method and Comparative Example 1 is that 1.197 g of water is completely replaced with bacterial cellulose dispersant. The types and amounts of other components, experimental steps, and reaction times are the same as those in Comparative Example 1.

[0067] Experimental results show that, compared with Comparative Example 1, when the amount of bacterial cellulose (BC) added is too low, the reinforcing and toughening effect of the nanofiber network is not significant, and the coating's anti-swelling and mechanical strength are insufficient. If the amount of bacterial cellulose dispersant added is further increased based on Example 7, the BC fibers are prone to agglomeration, affecting the coating's light transmittance and surface smoothness, and interfering with the uniformity of the photopolymerization reaction.

[0068] This invention, drawing on the structural features of deep-sea fish corneas, fish skin mucus, and mussel adhesion mechanisms, constructs a hydrophilic-hydrophobic heteropolymer network. This network achieves rapid water spreading and anti-swelling properties, possesses contact-active antibacterial and self-cleaning characteristics, and forms a stable Si-O-Si covalent interface for excellent substrate adhesion. Of particular note is the coating's sustained and stable anti-fogging performance with increasing thickness when in contact with water vapor over a wide temperature range of 20–100°C. The optimized AFH-3 sample integrates high optical transparency, excellent anti-fogging performance, low volume expansion rate, outstanding biocompatibility, and strong interfacial adhesion within the same system. It also exhibits stable wet-dry cycling performance, highly effective antibacterial effects, and a unique hybrid failure mode that allows for strong bonding with various transparent substrates. This hierarchical, bio-inspired design approach establishes a universal design paradigm for high-performance transparent medical optical coatings. The prepared coating shows broad application prospects in the functionalization of optical device surfaces, laying a reliable material foundation for the development of safer and more durable medical optical components.

[0069] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A double-bond-terminated cationic organosilicon waterborne polyurethane, characterized in that: Its structural formula is as follows: ， Where n is a positive integer, and n≥1.

2. The method for preparing double-bond-terminated cationic organosilicon aqueous polyurethane as described in claim 1, characterized in that: It is prepared by reacting triethylene glycol, 3-dimethylamino-1,2-propanediol, hydroxypropyl silicone oil, isophorone diisocyanate, chain extender bis(2-hydroxyethyl) disulfide, and end-capping agent hydroxyethyl methacrylate in a molar ratio of 35-36:32-33:1:100:13-14:36-37.

3. The preparation method of the double-bond-terminated cationic organosilicon waterborne polyurethane as described in claim 2, characterized in that: The reaction is specifically as follows: Isophorone diisocyanate, hydroxypropyl silicone oil, tetraethylene glycol, and 3-dimethylamino-1,2-propanediol were reacted under nitrogen protection in the presence of a catalyst and a viscosity modifier to prepare terminal isocyanate prepolymers. After reacting the chain extender bis(2-hydroxyethyl) disulfide with the isocyanate prepolymer, the end-capping agent hydroxyethyl methacrylate is added and reacted.

4. The preparation method of the double-bond-terminated cationic organosilicon aqueous polyurethane as described in claim 3, characterized in that: The catalyst comprises one or more of dibutyltin di(dodecanedioate), bismuth neodecanoate, stannous octanoate, triethylenediamine, and zirconium isooctanoate; the amount of the catalyst added is 0.5-2% of the total mass of isophorone diisocyanate, hydroxypropyl silicone oil, tetraethylene glycol, and 3-dimethylamino-1,2-propanediol; The viscosity modifier includes one or more of acetone, methyl acrylate, methyl methacrylate, ethyl lactate, 2-methyltetrahydrofuran, butanone, and cyclohexanone; the amount of the viscosity modifier added is 50-90% of the total mass of isophorone diisocyanate, hydroxypropyl silicone oil, tetraethylene glycol and 3-dimethylamino-1,2-propanediol.

5. The method for preparing double-bond-terminated cationic organosilicon aqueous polyurethane as described in claim 3 or 4, characterized in that: The reaction is carried out under nitrogen protection at a temperature of 70-90°C for 2-5 hours. The reaction involving the addition of the chain extender bis(2-hydroxyethyl) disulfide is carried out at a temperature of 60-80°C and a reaction time of 0.5-2 hours. The reaction involving the addition of the capping agent hydroxyethyl methacrylate takes place at a temperature of 60-80°C for 0.5-2 hours.

6. A method for preparing an anti-fogging and sterilizing hydrogel, characterized in that: include, Acrylamide and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide were dissolved in a solvent, and hydroxyethyl methacrylate, sodium polystyrene sulfonate, silane coupling agent and the double-bond-terminated cationic organosilicon waterborne polyurethane as described in claim 1 were added in sequence. 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, an ultraviolet photoinitiator, was added, and the mixture was uniformly dispersed in the dark.

7. The method for preparing the anti-fogging and sterilizing hydrogel as described in claim 6, characterized in that: By weight, it includes 0.5 to 3 parts of hydroxyethyl methacrylate, 0.5 to 3 parts of acrylamide, 0.1 to 1 part of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonylpropyl)ammonium hydroxide, 0.01 to 0.5 parts of sodium polystyrene sulfonate, 0 to 0.2 parts of silane coupling agent, 0.1 to 10 parts of double-bond-terminated cationic organosilicon waterborne polyurethane, and 0.1 to 3 parts of ultraviolet photoinitiator.

8. The method for preparing the anti-fogging and sterilizing hydrogel as described in claim 6, characterized in that: The silane coupling agent includes one or two of 3-(trimethoxysilyl)methacrylate and acryloyloxypropyltrimethoxysilane; The ultraviolet photoinitiator includes one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-2-methyl-1-phenylacetone, lithium phenyl(2,4,6-trimethylbenzoyl)phosphonate, and 1-hydroxycyclohexylphenyl ketone; The solvent is one or both of water and bacterial cellulose dispersant.

9. The anti-fogging sterilization hydrogel obtained by the preparation method according to any one of claims 6 to 8.

10. An anti-fogging and sterilization coating, characterized in that: The anti-fog sterilization hydrogel as described in claim 9 is uniformly coated onto a substrate and cured by ultraviolet irradiation.

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