Novel antifouling developing coating material as well as preparation method and application thereof

Abstract

The invention provides a novel anti-fouling developing coating material and a preparation method and application thereof, the anti-fouling developing coating material has a structure as shown in a formula I. Compared with a traditional developing coating, the novel anti-fouling developing coating material has higher medical safety, can ensure the stability and durability of a developing effect, and can be used for preparing an anti-fouling developing coating. And the method has a wider application range.

Description

[0001] This application claims the priority of the patent application with the application number 202311578586.5. The filing date of the prior application is November 24, 2023, and the invention title is A New Type of Anti-Fouling Developing Coating Material and Its Preparation Method and Application. Technical Field

[0002] The present invention belongs to the technical field of medical materials and relates to a new type of anti-fouling developing coating material and its preparation method and application. Background Art

[0003] Medical developing coatings play a crucial role in medical imaging. With the progress of medical imaging, higher requirements are put forward for the safety and developing effect of developing coatings. Medical developing coatings must have excellent anti-fouling ability to effectively resist the adhesion of bacterial proteins, prevent bacterial infections and cross-infections, and at the same time maintain a clean and transparent surface to ensure clear and accurate images. Secondly, medical developing coatings need to have clear and accurate developing ability.

[0004] I. Importance and Research Progress of Anti-Fouling Performance:

[0005] Medical anti-fouling developing coatings originated from the improvement of traditional developing coatings. Although traditional developing coatings provide developing functions, their anti-fouling properties are limited. With the increasing use of medical devices, the demand has become more urgent. Therefore, scientists began to study the addition of anti-fouling materials to improve anti-fouling performance. The anti-fouling principle mainly involves the hydrophilicity and lipophilicity of the material surface. A hydrophilic surface makes water form a large contact angle, so that water and impurities do not stay. A lipophilic surface prevents the attachment of organic substances or oils and reduces the adsorption of biomolecules.

[0006] In recent years, significant progress has been made in the research of medical anti-fouling coatings. Researchers have adjusted the surface properties to develop excellent anti-fouling coatings. For example, introducing superhydrophobic polymer materials to make the surface form a superhydrophobic effect, achieving efficient self-cleaning and anti-fouling. At the same time, bionic design of special surface structures, such as micro-nano concavities and convexities, honeycomb-like, reduces the surface contact area and reduces the attachment of pollutants. Embedding bioactive molecules into the coating to form a "bactericidal circle" to inhibit the reproduction of microorganisms and improve the anti-fouling effect.

[0007] II. Importance and Research Progress of Developing Performance:

[0008] The developing performance of medical anti-fouling developing coatings is crucial for the clarity and diagnostic accuracy of medical images. The developing coating needs to be sensitive to X-rays to ensure the developing effect under X-ray irradiation. Developing technology is widely used in medical imaging. Through the developing effect of imaging photosensitive materials, latent images are generated to form clear images. X-ray developing is a commonly used technology, which relies on the absorption and scattering of X-rays. The developing coating plays a key role in it, absorbing and scattering X-rays to generate images.

[0009] The research on medical imaging coatings has been continuously evolving with the progress of medical imaging technologies. Researchers have improved the imaging agents and the chemical composition of the coatings to enhance the imaging efficiency and image quality. Meanwhile, the introduction of new technologies such as nanotechnology and quantum dots has increased the sensitivity and selectivity of the coatings.

[0010] III. Challenges and Research Directions in Combining Imaging and Antifouling:

[0011] Combining the imaging and antifouling functions remains a challenge. While maintaining the imaging performance, excellent antifouling performance is required. However, the mutual influence between the imaging agent and the antifouling agent may reduce the imaging efficiency. More meticulous selection of coating materials and structural design are needed to achieve the optimal balance between imaging and antifouling performance. To address this challenge, researchers can explore various combinations of imaging agents and antifouling agents, and optimize the coating structure and chemical composition. Meanwhile, nanotechnology and surface engineering can be used to construct multifunctional imaging coatings to synergistically enhance the imaging and antifouling performance.

[0012] Generally speaking, medical imaging coatings are crucial in medical imaging. Through continuous research on improving the imaging performance and antifouling ability, it is expected to develop more advanced, safe, and reliable imaging coatings, providing better technical support for medical diagnosis and treatment. At the same time, the research on combining the imaging and antifouling functions is also expected to bring new breakthroughs to the development of medical imaging materials. Summary of the Invention

[0013] According to the current needs, the object of the present invention is to provide a novel antifouling imaging coating material, its preparation method, and applications. In order to develop imaging coatings with better performance, higher safety and reliability, and provide better technical support for medical diagnosis and treatment.

[0014] To achieve the object of the present invention, the following technical solutions are adopted:

[0015] On the one hand, the present invention provides a novel antifouling imaging coating material, and the novel antifouling imaging coating material has the structure as shown in Formula I below:

[0016]

[0017] Wherein, m = 1 - 40 (such as 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40, etc.), n = 1 - 40 (such as 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40, etc.), and k = 1 - 3 (such as 1, 2, or 3).

[0018] The anti-fouling and imaging coating material described in the present invention combines anti-fouling and imaging through covalent bonding technology, ensuring the stability of the material and the stability of the anti-fouling and imaging properties. This enables the material to have outstanding performance in both anti-fouling and imaging effects, making it have broad application prospects in the field of medical imaging and providing strong support for the safety of medical equipment and the accuracy of medical images.

[0019] In some preferred embodiments, the imaging agent is one or a mixture of at least two selected from iohexol, iohexol hydrolyzate, iopromide, meglumine diatrizoate, sodium diatrizoate, iodized oil, and iodixanol.

[0020] In a more preferred embodiment, the imaging agent is iohexol or iohexol hydrolyzate.

[0021] In some preferred embodiments, the imaging agent and the siloxane are connected through a linking group.

[0022] In some preferred embodiments, the imaging agent and the siloxane are connected by forming a Si-O-Si linkage bond.

[0023] In some preferred embodiments, the anti-fouling and imaging coating material has the structure shown in Formula II below:

[0024]

[0025] Wherein, m = 1 - 40 (such as 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40, etc.), n = 1 - 40 (such as 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40, etc.), k = 1 - 3 (such as 1, 2, or 3), R is selected from C1-C5 alkyl or C1-C5 alkylsilyl, and L is

[0026] In some preferred embodiments, m:n = 1:1 - 4:1, such as 1:1, 2:1, 3:1, or 4:1. In the present invention, within the range of m:n from 1:1 to 4:1, by adjusting the molar ratio of the modified choline phosphate polymer to the barium salt, the polymer material meeting the requirements of imaging and anti-fouling can be obtained.

[0027] In some preferred embodiments, m:n = 3:1.

[0028] On the other hand, the present invention provides a preparation method of the novel anti-fouling and imaging coating material as described above. The preparation method includes the following steps:

[0029] A hydrolysis polycondensation reaction is carried out between a developer modified with a siloxane reagent and a modified phosphorylcholine polymer modified with siloxane to obtain the novel antifouling developer coating material.

[0030] Preferably, the siloxane reagent is selected from

[0031] Preferably, the molar ratio of the developer modified with the siloxane reagent to the modified phosphorylcholine polymer modified with siloxane is 40:1 to 10:1, such as 40:1, 38:1, 35:1, 33:1, 30:1, 28:1, 25:1, 20:1, 18:1, 15:1, 13:1, 10:1, etc.

[0032] Preferably, the hydrolysis polycondensation reaction between the developer modified with the siloxane reagent and the modified phosphorylcholine polymer modified with siloxane is carried out at room temperature, and the reaction time is 12 to 48 h, such as 12 h, 14 h, 16 h, 18 h, 20 h, 24 h, 28 h, 30 h, 33 h, 35 h, 38 h, 40 h, 44 h or 48 h, preferably 24 h.

[0033] Preferably, the solvent for the hydrolysis polycondensation reaction between the developer modified with the siloxane reagent and the modified phosphorylcholine polymer modified with siloxane is a mixture of methanol and water, a mixture of isopropanol and water, or a mixture of DMSO and water.

[0034] Preferably, the developer modified with the siloxane reagent is prepared by the following preparation method:

[0035] The developer is reacted with the siloxane reagent in a mixed solvent to obtain the developer modified with the siloxane reagent;

[0036] Preferably, the molar ratio of the developer to the siloxane reagent is 1:1 to 3:1, such as 1:1, 1.5:1, 1.8:1, 2:1, 2.3:1, 2.5:1, 2.8:1 or 3:1.

[0037] Preferably, the temperature of the reaction between the developer and the siloxane reagent is room temperature, and the reaction time is 3 to 12 h, such as 3 h, 5 h, 8 h, 10 h, 11 h or 12 h, preferably 6 h.

[0038] Preferably, the mixed solvent is a mixture of methanol and water, a mixture of isopropanol and water, or a mixture of DMSO and water, and the volume ratio of the two solvents in the mixed solvent can be 1:1.

[0039] Preferably, the modified phosphorylcholine polymer modified with siloxane has the following structure:

[0040]

[0041] Among them, m = 1 to 40 (such as 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38 or 40, etc.), n = 1 to 40 (such as 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38 or 40, etc.), k = 1 to 3 (such as 1, 2 or 3), and R is selected from C1-C5 alkyl or C1-C5 alkylsilyl.

[0042] Preferably, the silicone-modified modified choline phosphate polymer is prepared by the following preparation method:

[0043] 2-Methacryloyloxyethyl choline phosphate reacts with a silicone compound to obtain the silicone-modified modified choline phosphate polymer.

[0044] Preferably, the silicone compound is methacryloyloxypropyl tris(trimethylsiloxy)silane and / or 3-(methacryloyloxy)propyltrimethoxysilane.

[0045] Preferably, the molar ratio of 2-methacryloyloxyethyl choline phosphate to the silicone compound is 40:1 to 10:1, such as 40:1, 38:1, 35:1, 33:1, 30:1, 28:1, 25:1, 20:1, 18:1, 15:1, 13:1, 10:1, etc.

[0046] Preferably, the reaction of 2-methacryloyloxyethyl choline phosphate with the silicone compound is carried out in the presence of 4-cyano-4-(thiobenzoyl)valeric acid.

[0047] Preferably, the reaction of 2-methacryloyloxyethyl choline phosphate with the silicone compound is carried out in the presence of an initiator.

[0048] Preferably, the initiator is selected from azobisisobutyronitrile.

[0049] Preferably, the temperature of the reaction of 2-methacryloyloxyethyl choline phosphate with the silicone compound is 60-70 °C, such as 60 °C, 63 °C, 65 °C, 68 °C or 70 °C, and the reaction time is 12 to 48 h, such as 12 h, 14 h, 16 h, 18 h, 20 h, 24 h, 28 h, 30 h, 33 h, 35 h, 38 h, 40 h, 44 h or 48 h, preferably 24 h.

[0050] Preferably, the reaction of 2-methacryloyloxyethyl choline phosphate with the silicone compound is carried out in a solvent, and the solvent is selected from n-propanol.

[0051] On the other hand, the present invention provides the application of the novel anti-fouling and imaging coating material as described above in coating the surface of a substrate.

[0052] Preferably, the substrate surface includes a silicon-based surface, a glass substrate surface, a metal substrate surface, and a polymer substrate surface.

[0053] The material of the present invention can be applied to the surfaces of various substrates, including glass substrates, metal substrates, and various plastic and polymer substrates (such as silicone rubber, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, etc.).

[0054] In the present invention, in the novel anti-fouling and imaging coating material, the imaging functional monomer and the anti-fouling functional polymer are connected by a silicon oxide compound, and the silicon oxide compound can bind more firmly to the substrate, thereby ensuring the stability and safety of the binding of the coating material of the present invention to the substrate. Especially in the case of a silicon-based substrate, the silicon oxide compound can be incorporated into the substrate material and even covalently bonded to the substrate material, further ensuring safety.

[0055] The present invention provides a design and preparation idea for a novel anti-fouling and imaging coating that can be applied to any substrate surface, preferably a silicon-based substrate surface. The design principle of the molecular structure is as Figure 1 shown. The molecular structure of the novel anti-fouling and imaging coating material involved in the present invention mainly includes two parts, namely an imaging functional monomer and an anti-fouling functional polymer. The imaging functional monomer uses a compound capable of covalently binding to phosphorylcholine, such as an intermediate molecule obtained by reacting an iodine-containing compound (such as the hydrolysis product of iohexol) with epoxy silane. This imaging functional monomer has excellent X-ray absorption performance and can produce accurate and clear imaging effects in medical imaging, providing reliable imaging information for medical contrast. The imaging functional monomer is tightly combined with the anti-fouling polymer modified phosphorylcholine containing a silane group through silane hydrolysis polymerization to form a composite structure while maintaining their respective characteristics. The introduction of the anti-fouling functional monomer endows the coating with excellent anti-fouling performance, which can effectively inhibit the adhesion of proteins and bacteria, thereby preventing the occurrence of bacterial infections and cross-infections. In scenarios with high hygiene standards such as medical devices and catheters, this anti-fouling performance is of great significance to ensure the hygiene and safety of medical devices. Through the combined action of the imaging functional monomer and the anti-fouling functional monomer, the novel anti-fouling and imaging coating forms a product with a silane group. This covalent bonding method enables the coating to have excellent stability on the silicon-based surface and will not be lost or peeled off over time, thereby significantly improving the durability and reliability of the imaging coating. At the same time, due to the universality of the silane group, this coating can be combined with the surfaces of various substrates, including glass substrates, metal substrates, and various plastic and polymer substrates (such as silicone rubber, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, etc.), providing wide applicability and flexibility for the application fields of the imaging coating.

[0056] The design concept of the anti-fouling and imaging material of the present invention combines the imaging function and the anti-fouling function ingeniously. By reasonably selecting monomers and achieving covalent bonding, the coating has the imaging ability and anti-fouling performance. This design concept has universality and operability, providing a new direction for the research and application of medical imaging materials in medical imaging, and bringing more progress and breakthroughs to the field of medical diagnosis and treatment.

[0057] On the other hand, the present invention provides an anti-fouling and imaging coating, and the preparation raw materials of the anti-fouling and imaging coating include the novel anti-fouling and imaging coating material as described above.

[0058] In the novel anti-fouling and imaging coating, the mixing mass ratio of the imaging functional monomer to the anti-fouling functional polymer is 2:1, 1:1, or 1:2. In the preparation of the anti-fouling and imaging coating, the anti-fouling and imaging coating material needs to be dissolved in a solvent (such as n-propanol) so that the concentration of the anti-fouling and imaging coating material is 400 mg / mL.

[0059] On the other hand, the present invention provides the application of the novel anti-fouling and imaging coating material as described above in medical devices or medical materials, optical lenses, or industrial printing.

[0060] The coating material of the present invention can be applied to the anti-fouling and imaging functional coating of medical devices, enabling the coated object to have both anti-fouling and X-ray imaging functions. The novel anti-fouling and imaging coating of the present invention can also be further applied to the coating of optical lenses and the anti-fouling and imaging functional coating in the field of industrial printing.

[0061] Compared with the prior art, the present invention has the following beneficial effects:

[0062] The anti-fouling coating prepared on a medical device using the novel anti-fouling and imaging coating material of the present invention has excellent anti-fouling performance. Compared with the traditional imaging coating, it has a significant improvement in anti-fouling. This coating contains a unique anti-fouling agent component, which can effectively resist the adhesion of bacterial proteins and prevent the occurrence of bacterial infection and cross-infection. This characteristic is crucial for medical safety, ensuring the hygiene and safety of medical equipment during use. The improvement of the imaging coating makes it applicable to various medical scenarios, especially for equipment such as operating rooms and medical catheters that require high hygiene standards, which has special significance.

[0063] Secondly, the novel anti-fouling and imaging coating shows excellent imaging effect. Compared with the traditional imaging coating, it achieves covalent bonding with the substrate and will not flow into the body's own metabolism, ensuring the stability and durability of the imaging effect, eliminating the possible side effects caused by the imaging coating, and improving the safety of the medical imaging coating. It has a positive significance for the health and medical experience of patients.

[0064] In addition, the novel anti-fouling and imaging-developing coating of the present invention has universality. Through silane bond polymerization, the coating can achieve covalent bonding with any silicon-based substrate, including various silicon-based surfaces such as glass, silica gel sheets, marble, etc., and is widely applicable to different clinical and laboratory scenarios to meet the needs of different users. Its preparation method is simpler and has lower cost compared with traditional coatings, providing a feasible way for the large-scale application of imaging-developing coatings.

[0065] In summary, the innovation of this novel anti-fouling and imaging-developing coating lies in the successful combination of anti-fouling and imaging development, solving the challenges in this field. Traditional imaging-developing coatings often make compromises between imaging development effects and anti-fouling performance, while the novel coating ingeniously integrates the two through covalent bonding technology. This provides a new direction for the research and development of medical imaging materials and offers a more innovative solution. The novel anti-fouling and imaging-developing coating performs excellently in terms of anti-fouling performance, imaging development effects, universality, and innovation. Its superior performance enables it to have broad application prospects in the field of medical imaging, providing strong support for the safety of medical equipment and the accuracy of medical images. Through continuous research and innovation, it is believed that the novel anti-fouling and imaging-developing coating will bring more progress and breakthroughs to medical diagnosis and treatment. Brief Description of the Drawings

[0066] Figure 1 is a schematic diagram of the design principle of the novel anti-fouling and imaging-developing coating;

[0067] Figure 2 is the nuclear magnetic test result of the imaging-developing compound used to prepare the novel anti-fouling and imaging-developing coating;

[0068] Figure 3 is the X-ray photoelectron spectroscopy test result of the imaging-developing compound used to prepare the novel anti-fouling and imaging-developing coating;

[0069] Figure 4 is the nuclear magnetic spectrum of the imaging-developing molecule of the comparative example of sodium diatrizoate combined with amino silane;

[0070] Figure 5 is the nuclear magnetic spectrum of the imaging-developing molecule of the comparative example of ioversol combined with 3-glycidoxypropyltrimethoxysilane;

[0071] Figure 6 is the nuclear magnetic spectrum of the imaging-developing molecule obtained by the combination of iohexol and isocyanate group silane through an ester bond;

[0072] Figure 7A is the imaging development effect diagram of the novel anti-fouling and imaging-developing coating;

[0073] Figure 7B is the quantitative analysis result diagram of the gray value of the imaging development effect of the novel anti-fouling and imaging-developing coating;

[0074] Figure 8AFluorescence microscope image of the novel anti-fouling and developing coating against protein adhesion;

[0075] Figure 8B Graph of the results of fluorescence quantitative analysis of the novel anti-fouling and developing coating against protein adhesion;

[0076] Figure 9A SEM image of the test results of the novel anti-fouling and developing coating against bacterial adhesion;

[0077] Figure 9B Graph of the results of colony quantitative analysis of the novel anti-fouling and developing coating against bacterial adhesion;

[0078] Figure 10A Graph of the test results of the novel anti-fouling and developing coating for imaging inside rat and pork tissues;

[0079] Figure 10B Graph of the results of quantitative analysis of the novel anti-fouling and developing coating for imaging inside rat tissues;

[0080] Figure 10C Graph of the results of quantitative analysis of the novel anti-fouling and developing coating for imaging inside pork tissues. Detailed implementation manners

[0081] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the specific embodiments and drawings of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0082] In the description of the present invention, it should be noted that the orientation or positional relationships indicated by the terms "upper", "lower", "inner", "outer", "front end", "rear end", "both ends", "one end", "the other end", etc. are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus cannot be construed as a limitation of the present invention. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance.

[0083] In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, the terms "installed", "provided with", "connected", etc. should be understood in a broad sense. For example, "connected" can be a fixed connection, a detachable connection, or an integral connection; it can also be indirectly connected through an intermediate medium, and can be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations.

[0084] Example 1 Synthesis example of modified choline phosphate.

[0085]

[0086] 2-Methacryloyloxyethyl choline phosphate (3 g), 4-cyano-4-(thiobenzoyl) pentanoic acid (3 g), and azobisisobutyronitrile (0.16 g) were dissolved in n-propanol (100 ml). The temperature was slowly raised to 65 °C under nitrogen protection, and the mixture was stirred and reacted for 24 h. Then, methacryloyloxypropyl tris(trimethylsiloxy)silane (8 ml) was added, and the reaction was continued for 24 h. The obtained n-propanol solution was added to ether (200 ml) for precipitation, and the precipitate was filtered and dried to obtain a choline phosphate polymer.

[0087] Example 2 Preparation example of a novel antifouling and developing coating material

[0088] a) Iohexol hydrolyzate (5 g) was dissolved in a 10 ml methanol / water binary mixed solvent (1:1), and potassium hydroxide (1.67 g) was added. The mixture was stirred and sonicated at room temperature to dissolve it completely to obtain a pale yellow solution; was dissolved in a 10 ml methanol / water binary mixed solvent, and then it was mixed with the pale yellow solution and stirred overnight at room temperature. Then, the reaction product was extracted from the methanol / water binary solvent into the organic phase with ethyl acetate, and the extraction was repeated 5 times. Then, the reaction mixture was evaporated with a rotary evaporator to remove the organic solvent, and after dialysis and liquid phase treatment, a silicon-based modified developing functional monomer C 27 H 44 I 3 N 3 O 13 Si.

[0089] b) The developing functional monomer in a) was mixed with modified choline phosphate in different molar ratios (i.e., 2:1, 1:1, and 1:2) in a methanol / water binary solvent (the volume ratio of methanol / water was 1:1). The mixture was stirred thoroughly for 6 h at room temperature to allow the silyl groups of the antifouling molecule modified choline phosphate to hydrolyze and polymerize completely. After extraction with an organic solvent and purification methods such as rotary evaporation, an antifouling and developing polymer ( Figure 1 ) was obtained.

[0090] Example 3 Tests of the present invention in terms of basic characterization of compounds

[0091] To determine whether the prepared novel antifouling and developing material was successfully synthesized and its elemental composition, we performed proton nuclear magnetic resonance ( 1 HNMR, deuterated chloroform) and X-ray photoelectron spectroscopy (XPS) tests on all samples. As Figure 2As shown, the proton nuclear magnetic resonance spectrum curve has vibration peaks at 7.3 ppm and 3.55 ppm, corresponding to the iodobenzene group in the imaging monomer and the siloxane group in the antifouling molecule respectively, which proves the successful synthesis of the antifouling imaging polymer material; as Figure 3 shown, peaks are detected in the XPS curve at 285 eV, 532 eV, 400 eV, and 620 eV, corresponding to C, O, N, and I elements respectively. And as the proportion of the iodine-containing imaging monomer increases, the I element content in the sample rises from 2.59% to 4.2%, which proves the successful polymerization of the iodine-containing imaging monomer and the antifouling molecule-modified choline phosphate.

[0092] Example 4

[0093] a) Dissolve sodium diatrizoate (5 g) in 10 ml of ethanol / water binary mixed solvent (1:1), then add O-benzotriazol-1-yl-N,N,N',N'-tetramethyluronium hexafluorophosphate (0.85 g) and triethylamine (600 μl), stir and sonicate at room temperature to fully dissolve to obtain a colorless solution; dissolve (3-aminopropyl)triethoxysilane (2 g) in 10 mL of ethanol solvent, then mix it with the colorless solution and stir overnight at room temperature. Then extract the reaction product into the organic phase with ethyl acetate, repeat the extraction 5 times. Then evaporate the reaction mixture with a rotary evaporator to remove the organic solvent, and then after dialysis and liquid phase treatment, an imaging molecule combined with sodium diatrizoate and amino silane is obtained. The nuclear magnetic data of the obtained molecule is as Figure 4 shown.

[0094] b) Mix the imaging molecule in a) with modified choline phosphate in different ratios (i.e., 2:1, 1:1, and 1:2) in a methanol / water binary solvent (the volume ratio of methanol / water is 1:1), and hydrolyze and polymerize to synthesize the antifouling imaging polymer.

[0095] Example 5

[0096] a) Dissolve iopamidol (5 g) in 10 mL of methanol / water binary mixed solvent (1:1), then add potassium hydroxide (1.67 g), stir and sonicate at room temperature to fully dissolve to obtain a light yellow solution; dissolve 3-glycidoxypropyltrimethoxysilane (2 g) in 10 mL of methanol / water binary mixed solvent, then mix it with the light yellow solution and stir overnight at room temperature. Then extract the reaction product from the methanol / water binary solvent into the organic phase with ethyl acetate, repeat the extraction 5 times. Then evaporate the reaction mixture with a rotary evaporator to remove the organic solvent, and then after dialysis and liquid phase treatment, an imaging functional monomer is obtained. The nuclear magnetic data is as Figure 5 shown.

[0097] b) The developing molecules in a) and the modified choline phosphate are mixed in different ratios (i.e., 2:1, 1:1, and 1:2) in a methanol / water binary solvent (the volume ratio of methanol / water is 1:1), and hydrolytic polymerization is carried out to synthesize the antifouling developing polymer.

[0098] Comparative Example 1

[0099] Iohexol (5 g) was dissolved in 10 ml of a methanol / water binary mixed solvent (1:1), and then potassium hydroxide (1.67 g) was added and stirred and sonicated at room temperature to fully dissolve it to obtain a pale yellow solution; 3-isocyanatopropyltriethoxysilane (2 g) was dissolved in 10 ml of a methanol / water binary mixed solvent, and then it was mixed with the pale yellow solution and stirred overnight at room temperature. Then, the reaction product was extracted from the methanol / water binary solvent into the organic phase with ethyl acetate, and the extraction was repeated 5 times. Then, the reaction mixture was evaporated using a rotary evaporator to remove the organic solvent, and then after dialysis and liquid phase treatment, the developing functional monomer obtained by the reaction of isocyanate and alcohol hydroxyl group was obtained, and the NMR data is as Figure 6 shown. Since the bonding mode was changed from a silane bond to an ester bond, the ester bond is unstable and prone to hydrolysis, and the NMR peaks shifted.

[0100] Example 6 Testing of the antifouling developing polymer coatings synthesized with different ratios of components in the present invention in terms of developing effect.

[0101] In terms of the developing effect, a medical X-ray irradiator was used to test the developing effect of the antifouling developing coating. The control groups were a blank negative control and a positive control of a platinum metal ring. The ratios of different raw material components were adjusted to optimize the developing effect of the coating. As Figure 7A and Figure 7B shown, the mass ratios of the developing molecule iohexol to the antifouling molecule modified choline phosphate in the experimental groups were 2:1, 1:1, and 1:2 respectively. It can be seen from Figure 7A that the developing performance was significantly enhanced with the increase in the proportion of iohexol, and when the proportion of iohexol was relatively high, the developing performance was comparable to that of platinum metal, indicating that the developing performance of the antifouling developing coating was excellent and could form a clear image under X-rays. Then, the imageJ software was used to quantitatively analyze the gray value of the coating developing effect ( Figure 7B ), and the control groups were a blank negative control and a positive control of a platinum metal ring. As Figure 7B shown, the developing gray value was proportional to the content of iohexol, and the gray value was the largest and the developing effect was the best when the component ratio was 4:1, showing a developing performance comparable to that of the platinum metal ring.

[0102] Example 7 Testing of the protein adhesion resistance of the antifouling developing polymer coating in the present invention.

[0103] In terms of anti - protein adsorption, the adsorption capacities of fibrin (FIB), serum protein (HB), and collagen (Col) on the antifouling imaging coating were measured and characterized. The ratio of imaging molecules to antifouling molecules in the antifouling imaging coating molecules used was 1:2. The protein molecules used were pre - modified with fluorescent molecules and adsorbed for 21 days. At 1, 3, 7, and 21 days (marked as day1, day3, day7, day21 in Figure 8B ), the adsorption of various molecules on the coating was observed using a fluorescence microscope (instrument model: FV3000 - Olympus, origin: Japan, manufacturer: Olympus). The control group was a blank control without the antifouling imaging coating ( Figure 8A and Figure 8B 's uncoating, and the coated group was represented by coating). As shown in Figure 8A , compared with the blank control, this coating demonstrated excellent anti - protein adsorption ability. Serum protein hardly adsorbed on the coating, and the adsorption amount of fibrin on the antifouling imaging coating was also extremely small, while the blank control group was covered with adsorbed protein molecules. Further, we performed fluorescence quantitative analysis on the total amount of adsorbed molecules ( Figure 8B ). Compared with the blank control group, the total amount of proteins adsorbed on the antifouling imaging coating was significantly reduced, demonstrating the super anti - protein adsorption ability of the antifouling imaging coating.

[0104] Example 6: Test on the anti - bacterial adhesion of the antifouling imaging polymer coating in the present invention.

[0105] In terms of anti - bacterial adhesion, we used Candida albicans (C.albicans), Escherichia coli (E.coli), and Staphylococcus aureus (S.aureus) to characterize the anti - bacterial adsorption ability of the antifouling imaging polymer coating. The ratio of imaging molecules to antifouling molecules in the antifouling imaging coating molecules used was 1:2. After the samples were soaked in high - concentration (108 / mL) solutions of the three kinds of bacteria for 2 weeks, they were taken out and dried, and the number of bacteria on them was observed using SEM. The bacterial solutions were live bacterial solutions, and the solvent was dialysis fluid. The live bacteria were changed every three days to ensure the bacterial activity. As shown in Figure 9A , after the adsorption of the three different bacteria, obvious large colonies existed on the control group without the antifouling imaging coating after 2 weeks, while no obvious colony growth was observed on the samples coated with the antifouling imaging coating. Further, we performed quantitative analysis on the adsorbed colonies ( Figure 9B ). The samples using the antifouling imaging coating significantly reduced bacterial adhesion, and the reduction rate of bacterial adhesion reached 95% after 2 weeks.

[0106] Example 7: Imaging test of the antifouling imaging polymer in rat and pork tissues in the present invention.

[0107] The anti-fouling imaging coating was applied to a silicone catheter with a diameter of 0.5 mm. The catheter was inserted into the internal parts of rat and pork tissues. A medical X-ray irradiator (manufacturer: FrameView Semiconductor Co., Ltd.; model: XVS2530) was used to take pictures of the sides and fronts of the rats and pork. The control group was a blank negative control. The mass ratios of the imaging molecule iohexol to the anti-fouling molecule modified choline phosphate in the experimental groups were 2:1, 1:1, and 1:2 respectively. As Figure 10A shown, the imaging anti-fouling coating had obvious imaging effects in the internal parts of both rat and pork tissues and clearly formed images under the X-ray irradiator. As Figure 10B and Figure 10C shown, through quantitative analysis of the imaged parts using Image J software, it was found that the imaging intensity in the internal parts of rats and pork increased significantly with the increase in the proportion of iohexol.

[0108] The applicant declares that the present invention uses the above embodiments to illustrate the novel anti-fouling imaging coating material, its preparation method and application of the present invention. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of the raw materials selected for the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. An antifouling developing coating material, characterized in that: The anti-fouling developing coating material has a structure as described in Formula I below: Among them, m=1~40, n=1~40, k=1~3.

2. The antifouling developing coating material according to claim 1, characterized in that: The developer is one selected from iohexol, iohexol hydrolyzate, iopromide, diatrizoate, sodium diatrizoate, iodized oil and iodixanol, or a mixture of at least two of them, preferably iohexol or iohexol hydrolyzate.

3. The antifouling developing coating material according to claim 1 or 2, characterized in that: The developer and the siloxane are connected via a connecting group; Preferably, the developer and siloxane are connected by forming a Si-O-Si bond.

4. The antifouling developing coating material according to any one of claims 1 to 3, characterized in that: The antifouling developing coating material has the following structure: Wherein, m=1-40, n=1-40, k=1-3, R is selected from C1-C5 alkyl or C1-C5 alkylsilyl, L is 5. The antifouling developing coating material according to any one of claims 1 to 4, characterized in that: m:n=1:1 to 4:1, more preferably m:n=3:

1.

6. The method for preparing an antifouling developing coating material according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: The developer modified by siloxane reagent is subjected to hydrolysis and polycondensation reaction with the modified phosphorylcholine polymer modified by siloxane to obtain the novel antifouling developing coating material.

7. The preparation method according to claim 6, characterized in that: The siloxane agent is selected from One or a combination of at least two of 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; Preferably, the molar ratio of the developer modified by the siloxane reagent to the modified phosphorylcholine polymer modified by the siloxane is 40:1 to 10:1; Preferably, the hydrolysis and polycondensation reaction of the developer modified by the siloxane reagent and the modified phosphorylcholine polymer modified by the siloxane is carried out at room temperature, and the reaction time is 12 to 48 hours; Preferably, the solvent for the hydrolysis and polycondensation reaction of the developer modified by the siloxane reagent and the modified phosphorylcholine polymer modified by the siloxane reagent is a mixture of methanol and water, a mixture of isopropanol and water, or a mixture of DMSO and water; Preferably, the siloxane reagent modified developer is prepared by the following preparation method: reacting a developer with a siloxane reagent in a mixed solvent to obtain a developer modified with the siloxane reagent; Preferably, the molar ratio of the developer to the siloxane agent is 1:1 to 3:1, preferably 2:1; Preferably, the temperature of the reaction of the developer and the siloxane reagent is room temperature, and the reaction time is 3h to 12h, preferably 6h; Preferably, the mixed solvent is a mixture of methanol and water, a mixture of isopropanol and water, or a mixture of DMSO and water; Preferably, the siloxane-modified modified phosphorylcholine polymer has a structure as shown in the following formula III: Wherein, m=1-40, n=1-40, k=1-3, and R is selected from a C1-C5 alkyl group or a C1-C5 alkylsilyl group.

8. Use of the novel antifouling developing coating material according to any one of claims 1 to 5 in coating a substrate surface; Preferably, the substrate surface includes a silicon-based surface, a glass-based surface, a metal-based surface, or a high-molecular polymer-based surface.

9. An antifouling developing coating, characterized in that: The raw materials for preparing the anti-fouling developing coating include the novel anti-fouling developing coating material according to any one of claims 1 to 5.

10. Use of the novel antifouling developing coating material according to any one of claims 1 to 5 in medical devices or medical materials, optical lenses or industrial printing.

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