Super-hydrophilic anti-fouling silicone rubber composite material and preparation method thereof

Abstract

The invention discloses a super-hydrophilic anti-fouling silicone rubber composite material. The silicone rubber composite material comprises the following raw material components: a silicone rubber composite body material containing vinyl and a hydrophilic solution, the vinyl-containing silicone rubber composite body material comprises the following raw material components in percentage by mass: 30-40wt% of vinyl-containing silicone rubber, 20-40wt% of vinyl-containing silicone rubber, 20-40wt% of vinyl-containing silicone rubber, 5- 29 wt%-40 wt% of a modified monomer; 29 wt%-40 wt% of an acrylic ester monomer; 0.1 wt% to 5 wt% of a photoinitiator; the hydrophilic solution is prepared from the following raw material components in percentage by mass: 5wt%-90wt% of a hydrophilic monomer; 0.1 wt% to 5 wt% of a photoinitiator; and the balance of solvent. The super-hydrophilic anti-fouling silicone rubber composite material has super-hydrophilicity, long-term hydrophilic stability and anti-fouling performance, the preparation method is simple and effective, the cost is low, and the super-hydrophilic anti-fouling silicone rubber composite material has a very good medical instrument application prospect.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically to a superhydrophilic and antifouling silicone rubber composite material and its preparation method. Background Technology

[0002] Silicone rubber possesses excellent biocompatibility and chemical stability, making it widely used in biomedical devices such as artificial heart valves, intraocular lenses, artificial meninges, cochlear implants, artificial lung membranes, artificial fingers, artificial joints, and artificial catheters. However, the inherent hydrophobicity of silicone rubber still presents several limitations in its clinical applications. For instance, its surface easily attracts bacteria, cells, viruses, or proteins, potentially leading to infections, inflammation, thrombosis, and calcification, thus restricting its further clinical use. Hydrophilic modification of silicone rubber can effectively improve its wettability and hydrophilic antifouling properties, thereby enhancing its effectiveness and safety in the medical field.

[0003] Currently, common methods for hydrophilic modification involve adding substances containing hydrophilic segments to the silicone rubber matrix to prepare silicone rubber with surface hydrophilicity. For example, grafting polydimethylsiloxane (PDMS) with the hydrophilic monomer N-vinylpyrrolidone (NVP) is a common method for hydrophilic modification of silicone rubber. However, when hydrophilic monomers such as NVP are directly reacted with PDMS, the low polarity of PDMS and the high polarity of NVP are immiscible, leading to stratification of the reaction system and difficulty in forming a uniform copolymer. This results in uneven distribution of hydrophilic groups within the PDMS matrix, leading to insufficient hydrophilicity on the PDMS surface. Furthermore, after long-term use, hydrophilic groups are prone to migration or loss, causing a significant decrease in the hydrophilicity of the material surface over time. In addition, a common method to address the insufficient hydrophilicity of materials is to construct micro / nano-rough structures on the material surface to achieve superhydrophilic properties; however, this method is difficult and complex to prepare, hindering its mass production. Therefore, finding a silicone rubber composite material with superhydrophilic properties that can maintain hydrophilic stability over a long period is key to solving the current technical problems. Summary of the Invention

[0004] To address current technical problems, this invention provides a superhydrophilic antifouling silicone rubber composite material and its preparation method. This silicone rubber composite material achieves superhydrophilic modification of the silicone rubber by constructing a stable hydrophilic coating on the surface of a new silicone rubber matrix after bulk hydrophilic modification, thereby maintaining its long-term hydrophilic stability. The superhydrophilic antifouling silicone rubber composite material of this invention exhibits excellent superhydrophilic and antifouling properties and long-term hydrophilic stability, solving the problems of existing technologies that require the introduction of micro / nano rough structures to achieve superhydrophilic performance, as well as insufficient superhydrophilic stability and antifouling performance.

[0005] To achieve the objectives of this invention, the following technical solution is adopted:

[0006] In a first aspect, the present invention provides a superhydrophilic and antifouling silicone rubber composite material, comprising the following raw material components:

[0007] Silicone rubber composite bulk material containing vinyl groups and aqueous solutions;

[0008] The vinyl-containing silicone rubber composite body material comprises the following raw material components by mass percentage:

[0009] 30wt%-40wt% of vinyl-containing silicone rubber;

[0010] Modified monomers 29wt%-40wt%;

[0011] Acrylic ester monomers 29wt%-40wt%;

[0012] Photoinitiator 0.1wt%-5wt%;

[0013] The aqueous solution comprises, by mass percentage, the following raw material components:

[0014] Hydrophilic monomers 5wt%-90wt%;

[0015] Photoinitiator 0.1wt%-5wt%;

[0016] The remainder is solvent.

[0017] In some embodiments of the present invention, the vinyl-containing silicone rubber comprises one or more of the following: vinyl-terminated dimethyl polysiloxane, vinyl-terminated methyl vinyl polysiloxane, divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane), vinyl-terminated methyl phenyl polysiloxane, vinyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane), vinyl-terminated methyl phenyl polysiloxane, or vinyl-terminated dimethylmethyl-3,3,3-trifluoropropyl (siloxane and polysiloxane).

[0018] In some embodiments of the present invention, the modified monomer includes one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, or N-vinylimidazolium ketone.

[0019] In some embodiments of the present invention, the acrylate monomers include one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, n-butyl methacrylate, or hydroxypropyl methacrylate.

[0020] In some embodiments of the present invention, the photoinitiator includes one or more of Irgacure 2959, Irgacure 184, Irgacure 907, Irgacure 1700, Darocure 1173 or Irgacure 819.

[0021] In some embodiments of the present invention, the hydrophilic monomer includes one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, or N-vinylimidazolium ketone.

[0022] In some embodiments of the present invention, the solvent includes anhydrous ethanol.

[0023] In some embodiments of the present invention, the surface water contact angle of the superhydrophilic antifouling silicone rubber composite material is 5-10°, preferably 5-9°.

[0024] Secondly, the present invention provides a method for preparing the superhydrophilic antifouling silicone rubber composite material as described above, comprising the following steps:

[0025] (1) A mixture is prepared by mixing vinyl-containing silicone rubber, modified monomer, acrylate monomer and photoinitiator, and the mixture is placed in a mold for photocuring to obtain a vinyl-containing silicone rubber composite body material;

[0026] (2) A hydrophilic solution is obtained by mixing the hydrophilic monomer, photoinitiator and solvent;

[0027] (3) The above-mentioned hydrophilic water solution is coated onto the vinyl-containing silicone rubber composite body material of step (1), and then photocured to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0028] In the preparation method of the present invention, step (3) can also be to impregnate the vinyl-containing silicone rubber composite body material in the hydrophilic water solution of step (2) and then perform photocuring to obtain a superhydrophilic antifouling silicone rubber composite material.

[0029] In the preparation method of the present invention, the mold in step (1) includes a polytetrafluoroethylene mold.

[0030] In the preparation method of the present invention, the photocuring in step (1) includes ultraviolet light curing.

[0031] In the preparation method of the present invention, the ultraviolet curing is further performed by irradiation under a 405nm / 100W ultraviolet lamp for 5 to 600 seconds.

[0032] In the preparation method of the present invention, the photocuring in step (3) includes ultraviolet light curing.

[0033] In the preparation method of the present invention, the ultraviolet curing is further performed by irradiation under a 405nm / 100W ultraviolet lamp for 5 to 600 seconds.

[0034] Thirdly, the present invention provides the application of the superhydrophilic antifouling silicone rubber composite material as described above or the silicone rubber composite material prepared by the above-described superhydrophilic antifouling silicone rubber composite material in the field of medical devices; preferably, the field of medical devices includes one or more of artificial heart valves, artificial lenses, artificial meninges, artificial cochleas, artificial lung membranes, artificial fingers, artificial joints or artificial catheters.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] 1. This invention first prepares a new vinyl-containing silicone rubber composite material by modifying monomers, and then uses an appropriate amount of hydrophilic monomers to construct a hydrophilic coating on the surface of the silicone rubber, thereby giving the silicone rubber superhydrophilic properties; avoiding the complex process in the prior art that requires the introduction of micro-nano rough structures to achieve superhydrophilic properties.

[0037] 2. The surface water contact angle of the superhydrophilic and antifouling silicone rubber composite material of the present invention is 5-10°, exhibiting superhydrophilicity and effectively inhibiting the migration of hydrophobic molecular chains of the silicone rubber matrix to the surface, thereby achieving long-term hydrophilic stability and antifouling performance.

[0038] 3. The superhydrophilic antifouling silicone rubber composite material provided by this invention has a simple and effective process, low cost, and very good application prospects in medical devices. Attached Figure Description

[0040] Figure 1 The surface water contact angle of the superhydrophilic silicone rubber composite material prepared in Example 1;

[0041] Figure 2 The surface water contact angle of the superhydrophilic silicone rubber composite material prepared in Example 8;

[0042] Figure 3 The surface water contact angle of the silicone rubber composite material prepared in Comparative Example 1;

[0043] Figure 4 The water contact angle of the surface of the hydrophilic silicone rubber composite material prepared in Comparative Example 2 is shown. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Any non-essential improvements and adjustments made by those skilled in the art based on the content of this invention should be considered within the scope of protection of this invention.

[0045] The inventors have achieved superhydrophilic modification of silicone rubber by constructing a stable hydrophilic coating on the surface of a new silicone rubber matrix after bulk hydrophilic modification. This significantly inhibits the migration of hydrophobic molecular chains from the silicone rubber matrix to the surface and maintains its long-term hydrophilic stability and antifouling properties.

[0046] Based on the above viewpoints, in a first aspect, the present invention provides a superhydrophilic and antifouling silicone rubber composite material, comprising the following raw material components:

[0047] Silicone rubber composite bulk material containing vinyl groups and aqueous solutions;

[0048] The vinyl-containing silicone rubber composite body material comprises the following raw material components by mass percentage:

[0049] 30wt%-40wt% of vinyl-containing silicone rubber;

[0050] Modified monomers 29wt%-40wt%;

[0051] Acrylic ester monomers 29wt%-40wt%;

[0052] Photoinitiator 0.1wt%-5wt%;

[0053] The aqueous solution comprises, by mass percentage, the following raw material components:

[0054] Hydrophilic monomers 5wt%-90wt%;

[0055] Photoinitiator 0.1wt%-5wt%;

[0056] The remainder is solvent.

[0057] In this invention, the vinyl-containing silicone rubber is a type of vinyl silicone rubber commonly used in the art, such as vinyl-terminated polysiloxanes, side-chain vinyl polysiloxanes, etc. In some embodiments of this invention, the vinyl-containing silicone rubber includes one or more of the following: vinyl-terminated dimethyl polysiloxane, vinyl-terminated methyl vinyl polysiloxane, divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane), vinyl-terminated methylphenyl polysiloxane, vinyl-terminated dimethylmethylvinyl (siloxane and polysiloxane), vinyl-terminated methylphenyl polysiloxane, or vinyl-terminated dimethylmethyl-3,3,3-trifluoropropyl (siloxane and polysiloxane). In some embodiments of this invention, in the vinyl-containing silicone rubber composite material, the content of the vinyl-containing silicone rubber, by mass percentage, is 30wt%-40wt%, preferably 30wt%-39wt%, more preferably 31wt%-39wt%, and more preferably 30wt%-38wt%.

[0058] In some embodiments of the present invention, the modified monomer includes one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, or N-vinylimidazolium ketone. In some embodiments of the present invention, the modified monomer is N-vinylpyrrolidone. In some embodiments of the present invention, in the vinyl-containing silicone rubber composite bulk material, the content of the modified monomer, by mass percentage, is 30wt%-40wt%, preferably 30wt%-39wt%, more preferably 31wt%-40wt%.

[0059] In some embodiments of the present invention, in the vinyl-containing silicone rubber composite bulk material, the photoinitiator includes one or more of Irgacure 2959, Irgacure 184, Irgacure 907, Irgacure 1700, Darocure 1173, or Irgacure 819. In some embodiments of the present invention, in the vinyl-containing silicone rubber composite bulk material, the photoinitiator is preferably Irgacure 2959, more preferably Irgacure 819. In some embodiments of the present invention, in the vinyl-containing silicone rubber composite bulk material, the content of the photoinitiator, by weight percentage, is 0.1wt%-4.9wt%, preferably 0.1wt%-4.8wt%, more preferably 0.2wt%-4.8wt%.

[0060] In some embodiments of the present invention, the photoinitiator in the aqueous solution comprises one or more of Irgacure 2959, Irgacure 184, Irgacure 907, Irgacure 1700, Darocure 1173, or Irgacure 819. In some embodiments of the present invention, the photoinitiator in the aqueous solution is preferably Irgacure 2959, more preferably Irgacure 819. In some embodiments of the present invention, the content of the photoinitiator in the aqueous solution, by mass percentage, is 0.1wt%-4.9wt%, preferably 0.1wt%-4.8wt%, more preferably 0.2wt%-4.8wt%.

[0061] In some embodiments of the present invention, the hydrophilic monomer includes one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, or N-vinylimidazolium ketone. In some embodiments of the present invention, the hydrophilic monomer is N-vinylpyrrolidone. In some embodiments of the present invention, the hydrophilic monomer content in the hydrophilic water solution is 5 wt%-89 wt%, preferably 5 wt%-87 wt%, and more preferably 6 wt%-88 wt%, by mass percentage.

[0062] In some embodiments of the present invention, the solvent includes anhydrous ethanol.

[0063] In some embodiments of the present invention, the surface water contact angle of the superhydrophilic antifouling silicone rubber composite material is 5-10°, preferably 5-9°.

[0064] In some embodiments of the present invention, a vinyl-containing silicone rubber composite bulk material and an aqueous solution are photocured to obtain a superhydrophilic, antifouling silicone rubber composite material. In some embodiments of the present invention, the photocuring includes ultraviolet light curing.

[0065] Secondly, the present invention provides a method for preparing the superhydrophilic antifouling silicone rubber composite material as described above, comprising the following steps:

[0066] (1) A mixture is prepared by mixing vinyl-containing silicone rubber, modified monomer, acrylate monomer and photoinitiator, and the mixture is placed in a mold for photocuring to obtain a vinyl-containing silicone rubber composite body material;

[0067] (2) A hydrophilic solution is obtained by mixing the hydrophilic monomer, photoinitiator and solvent;

[0068] (3) The above-mentioned hydrophilic water solution is coated onto the vinyl-containing silicone rubber composite body material of step (1), and then photocured to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0069] In the preparation method of the present invention, step (3) can also be to impregnate the vinyl-containing silicone rubber composite body material in the hydrophilic water solution of step (2) and then perform photocuring to obtain a superhydrophilic antifouling silicone rubber composite material.

[0070] In the preparation method of the present invention, the mold in step (1) includes a polytetrafluoroethylene mold.

[0071] In the preparation method of the present invention, the photocuring in step (1) includes ultraviolet light curing.

[0072] In the preparation method of the present invention, the ultraviolet curing is further performed by irradiation under a 405nm / 100W ultraviolet lamp for 5 to 600 seconds.

[0073] In the preparation method of the present invention, the photocuring in step (3) includes ultraviolet light curing.

[0074] In the preparation method of the present invention, the ultraviolet curing is further performed by irradiation under a 405nm / 100W ultraviolet lamp for 5 to 600 seconds.

[0075] Thirdly, the present invention provides the application of the superhydrophilic antifouling silicone rubber composite material as described above or the silicone rubber composite material prepared by the above-described superhydrophilic antifouling silicone rubber composite material in the field of medical devices; preferably, the field of medical devices includes one or more of artificial heart valves, artificial lenses, artificial meninges, artificial cochleas, artificial lung membranes, artificial fingers, artificial joints or artificial catheters.

[0076] The superhydrophilic and antifouling silicone rubber composite material of the present invention was tested using the following methods:

[0077] Water contact angle: The static water droplet contact angle of the sample surface is measured using a 5μL water droplet on a contact angle meter.

[0078] The specific methods for antibacterial testing are as follows:

[0079] (1) Cut the sample into 1 cm × 1 cm pieces for later use.

[0080] (2) Preparation of culture medium aqueous solution and sterilized water: Weigh 2.4 g of culture medium with an electronic balance and add it to a laboratory medicine bottle containing 100 mL of deionized water. Seal the bottle and shake it to form a uniform solution. Weigh 1000 mL of deionized water with another medicine bottle. Place the two medicine bottles in an autoclave for high-temperature sterilization. After sterilization, store them in a 4℃ refrigerator for later use.

[0081] (3) Sterilization of experimental materials: Before conducting the antimicrobial experiment, all instruments used for the antimicrobial test, such as centrifuge tubes, pipettes and tips, conical flasks, 24-well plates, cell culture dishes, PBS buffer and culture medium, must be placed in a biosafety cabinet for UV sterilization for 30 min. After sterilization, they should be placed in the sterilization room for later use. The silicone rubber sample from (1) should be rinsed with sterile PBS buffer, placed in a 24-well plate, and then placed in a biosafety cabinet for UV sterilization of both sides of the sample for 30 min each.

[0082] (4) Preparation of solid culture medium: Weigh 24 g of culture medium, 1000 mL of deionized water and 15 g of agar powder and add them to the medicine bottle and shake well by hand. Then place it in an autoclave for high-temperature sterilization. After taking it out, pour it into the sterilized cell culture dish, cool it for 4 h and then put it in a 4℃ refrigerator for later use.

[0083] (5) Preparation of bacterial culture: After activating the lyophilized bacterial strain in a biosafety cabinet, the culture was added to centrifuge tubes and incubated in a constant temperature shaker at 36.8℃ and 250 rpm to obtain the bacterial stock solution. The cultured bacterial solution was centrifuged at 2750 rpm for 5 min, and the absorbance at OD 600 nm (i.e., bacterial density) was measured using a UV spectrophotometer. When the absorbance was between 0.6 and 0.8 × 10⁻⁶, the bacterial density was determined. 5 The culture was completed when the concentration of CFU / mL was reached, and the target concentration of bacterial solution was obtained. The solution was then removed and stored in a 4°C refrigerator for later use.

[0084] (6) Bacterial co-culture: Add the target concentration of bacterial solution to the wells containing the samples in a sterilized 24-well plate, and then incubate in a 37°C bacterial incubator for 4 h. Three parallel samples are set up for each experiment. After the incubation is completed, add 1 mL of sterile PBS buffer to the wells containing the samples, seal and sonicate for 10 min. After the sonication is completed, the bacterial stock solution of each sample is obtained. Take a new 24-well plate, add 1 mL of sterile PBS buffer to each well, take 10 mL of bacterial stock solution from each well of the 24-well plate containing the bacterial culture samples, add it to the corresponding well plate, take 100-200 mL of diluted bacterial solution and spread it evenly on the solid culture medium, and incubate in a constant temperature incubator for 18-24 h.

[0085] After the culture was completed, the plate count method was used to take pictures and count the number of bacteria.

[0086] The formula for calculating the anti-adhesion rate is: Anti-adhesion rate R = (X0 - X) / X0 × 100%, where X0 is the number of plate colonies of the unmodified silicone rubber sample and X is the number of plate colonies of the modified sample.

[0087] The beneficial effects of the present invention will be further illustrated below with reference to embodiments and comparative examples. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0088] The manufacturers and brands of the raw materials used in Examples 1-9 and Comparative Examples 1-2 of this invention are shown in Table 1.

[0089] Table 1 lists the manufacturers and brands of the raw materials used in the examples and comparative examples:

[0090] raw material Manufacturer Brand Vinyl-terminated dimethyl polysiloxane Shanghai Aladdin Biochemical Technology Co., Ltd. 68083-19-2 Divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane) Shanghai Aladdin Biochemical Technology Co., Ltd. 68951-96-2 Vinyl-terminated methylphenyl polysiloxane Shanghai Bohr Chemical Reagent Co., Ltd. B643650 Vinyl-terminated dimethylmethyl-3,3,3-trifluoropropyl (siloxane and polysiloxane) Shanghai Yuanye Biotechnology Co., Ltd. 68951-98-4 N-vinylpyrrolidone Shanghai Aladdin Biochemical Technology Co., Ltd. 88-12-0 Isooctyl acrylate Shanghai Yuanye Biotechnology Co., Ltd. 106-63-8 Irgacure 2959 Shanghai Aladdin Biochemical Technology Co., Ltd. 106797-53-9 Irgacure 819 Shanghai Aladdin Biochemical Technology Co., Ltd. 162881-26-7 Irgacure 1700 Shanghai Aladdin Biochemical Technology Co., Ltd. 174285-64-4 Darocure1173 Merck Chemicals Co., Ltd. 7473-98-5 Anhydrous ethanol Chengdu Kelong Chemical Co., Ltd. 64-17-5

[0091] Example 1

[0092] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0093] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0094] Vinyl-terminated dimethyl polysiloxane 30 wt%;

[0095] N-vinylpyrrolidone 39wt%;

[0096] 30 wt% isooctyl acrylate;

[0097] Photoinitiator Irgacure 2959 1wt%;

[0098] The aqueous solution is prepared from the following raw material components by mass percentage:

[0099] 5 wt% N-vinylpyrrolidone

[0100] Photoinitiator Irgacure 2959 1wt%;

[0101] 94 wt% anhydrous ethanol.

[0102] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0103] (1) The corresponding amounts of vinyl-terminated dimethyl polysiloxane, N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Irgacure 2959 were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 100 s to obtain a vinyl-containing silicone rubber composite body material.

[0104] (2) The above-mentioned corresponding amounts of N-vinylpyrrolidone, photoinitiator Irgacure 2959 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution;

[0105] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 120 s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0106] Example 2

[0107] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0108] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0109] Vinyl-terminated dimethylmethyl-3,3,3-trifluoropropyl (siloxane and polysiloxane) 30 wt%;

[0110] N-vinylpyrrolidone 30wt%

[0111] Isooctyl acrylate 39.9 wt%;

[0112] Photoinitiator Irgacure 2959 0.1wt%;

[0113] The aqueous solution is prepared from the following raw material components by mass percentage:

[0114] N-vinylpyrrolidone 9.9 wt%

[0115] Photoinitiator Irgacure 2959 0.1wt%;

[0116] 90 wt% anhydrous ethanol.

[0117] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0118] (1) The vinyl-terminated dimethylmethyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Irgacure 2959 were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 600 s to obtain a vinyl-containing silicone rubber composite body material.

[0119] (2) The above-mentioned corresponding amounts of N-vinylpyrrolidone, photoinitiator Irgacure 2959 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution;

[0120] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 600 s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0121] Example 3

[0122] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0123] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0124] Vinyl-terminated methylphenyl polysiloxane 30 wt%;

[0125] 35 wt% N-vinylpyrrolidone;

[0126] 30 wt% isooctyl acrylate;

[0127] Photoinitiator Irgacure 819 5wt%;

[0128] The aqueous solution is prepared from the following raw material components by mass percentage:

[0129] 90 wt% N-vinylpyrrolidone

[0130] Photoinitiator Irgacure 819 5wt%;

[0131] 5 wt% anhydrous ethanol.

[0132] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0133] (1) The vinyl-terminated methylphenyl polysiloxane, N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Irgacure 819 of the above corresponding amounts were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the above mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 5 s to obtain a vinyl-containing silicone rubber composite body material.

[0134] (2) The corresponding amounts of N-vinylpyrrolidone, photoinitiator Irgacure 819 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution;

[0135] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 5 s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0136] Example 4

[0137] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0138] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0139] Divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane) 39.9 wt%;

[0140] N-vinylpyrrolidone 30wt%

[0141] 30 wt% isooctyl acrylate;

[0142] Photoinitiator Irgacure 1700 0.1wt%;

[0143] The aqueous solution is prepared from the following raw material components by mass percentage:

[0144] N-vinylpyrrolidone 39.9 wt%;

[0145] Photoinitiator Irgacure 1700 0.1wt%;

[0146] 60 wt% anhydrous ethanol.

[0147] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0148] (1) The corresponding amounts of divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane), N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Irgacure 1700 were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405 nm / 100 W ultraviolet lamp for 480 s to obtain a vinyl-containing silicone rubber composite body material.

[0149] (2) The above-mentioned corresponding amounts of N-vinylpyrrolidone, photoinitiator Irgacure 1700 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution;

[0150] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 480s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0151] Example 5

[0152] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0153] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0154] Vinyl-terminated dimethyl polysiloxane 30 wt%;

[0155] N-vinylpyrrolidone 39.9 wt%;

[0156] 30 wt% isooctyl acrylate;

[0157] Photoinitiator Darocure 1173 0.1wt%;

[0158] The aqueous solution is prepared from the following raw material components by mass percentage:

[0159] 55 wt% N-vinylpyrrolidone;

[0160] Photoinitiator Darocure1173 5wt%;

[0161] 40 wt% anhydrous ethanol.

[0162] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0163] (1) The corresponding amounts of vinyl-terminated dimethyl polysiloxane, N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Darocure1173 were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 480 s to obtain a vinyl-containing silicone rubber composite body material.

[0164] (2) The above-mentioned corresponding amounts of N-vinylpyrrolidone, photoinitiator Darocure1173 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution.

[0165] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 30 s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0166] Example 6

[0167] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0168] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0169] Vinyl-terminated dimethylmethyl-3,3,3-trifluoropropyl (siloxane and polysiloxane) 35 wt%;

[0170] N-vinylpyrrolidone 34.5 wt%;

[0171] 30 wt% isooctyl acrylate;

[0172] Photoinitiator Darocure 1173 0.5wt%;

[0173] The aqueous solution is prepared from the following raw material components by mass percentage:

[0174] N-vinylpyrrolidone 29.5 wt%;

[0175] Photoinitiator Darocure 1173 0.5wt%;

[0176] 70wt% anhydrous ethanol.

[0177] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0178] (1) The vinyl-terminated dimethylmethyl-3,3,3-trifluoropropyl (siloxane and polysiloxane), N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Darocure1173 were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 60 s to obtain a vinyl-containing silicone rubber composite body material.

[0179] (2) The above-mentioned corresponding amounts of N-vinylpyrrolidone, photoinitiator Darocure1173 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution.

[0180] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 60 s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0181] Example 7

[0182] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0183] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0184] Vinyl-terminated methylphenyl polysiloxane 32wt%;

[0185] 35 wt% N-vinylpyrrolidone;

[0186] 30 wt% isooctyl acrylate;

[0187] Photoinitiator Irgacure 1700 3wt%;

[0188] The aqueous solution is prepared from the following raw material components by mass percentage:

[0189] N-vinylpyrrolidone 47wt%

[0190] Photoinitiator Irgacure 1700 3wt%;

[0191] 50wt% anhydrous ethanol.

[0192] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0193] (1) The vinyl-terminated methylphenyl polysiloxane, N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Irgacure 1700 of the above corresponding amounts were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the above mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 180 s to obtain a vinyl-containing silicone rubber composite body material.

[0194] (2) The above-mentioned corresponding amounts of N-vinylpyrrolidone, photoinitiator Irgacure 1700 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution;

[0195] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 180 s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0196] Example 8

[0197] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0198] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0199] Divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane) 38 wt%;

[0200] 31 wt% N-vinylpyrrolidone;

[0201] Isooctyl acrylate 30.9 wt%;

[0202] Photoinitiator Irgacure 819 0.1wt%;

[0203] The aqueous solution is prepared from the following raw material components by mass percentage:

[0204] N-vinylpyrrolidone 14.9 wt%;

[0205] Photoinitiator Irgacure 819 0.1wt%;

[0206] 85 wt% anhydrous ethanol.

[0207] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0208] (1) The corresponding amounts of divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane), N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Irgacure 819 were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 300 s to obtain a vinyl-containing silicone rubber composite body material.

[0209] (2) The corresponding amounts of N-vinylpyrrolidone, photoinitiator Irgacure 819 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution;

[0210] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 300 s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0211] Example 9

[0212] A superhydrophilic and antifouling silicone rubber composite material is prepared by photocuring a vinyl-containing silicone rubber composite matrix material and a hydrophilic solution.

[0213] The vinyl-containing silicone rubber composite body material is prepared from the following raw material components by weight percentage:

[0214] Vinyl-terminated dimethyl polysiloxane 33 wt%;

[0215] N-vinylpyrrolidone 32wt%;

[0216] 30 wt% isooctyl acrylate;

[0217] Photoinitiator Irgacure 2959 5wt%;

[0218] The aqueous solution is prepared from the following raw material components by mass percentage:

[0219] N-vinylpyrrolidone 70wt%;

[0220] Photoinitiator Irgacure 2959 5wt%;

[0221] 25wt% anhydrous ethanol.

[0222] The preparation method of the above-mentioned superhydrophilic antifouling silicone rubber composite material includes the following steps:

[0223] (1) The corresponding amounts of vinyl-terminated dimethyl polysiloxane, N-vinylpyrrolidone, isooctyl acrylate and photoinitiator Irgacure 2959 were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 30 s to obtain a vinyl-containing silicone rubber composite body material.

[0224] (2) The above-mentioned corresponding amounts of N-vinylpyrrolidone, photoinitiator Irgacure 2959 and anhydrous ethanol were placed in a constant temperature magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a hydrophilic solution;

[0225] (3) The hydrophilic water solution from step (2) is coated onto the vinyl-containing silicone rubber composite body material obtained in step (1), and then cured under a 405nm / 100W ultraviolet lamp for 30 s to obtain a super-hydrophilic anti-fouling silicone rubber composite material.

[0226] Comparative Example 1

[0227] A vinyl-containing silicone rubber composite bulk material is prepared from the following raw material components by mass percentage:

[0228] Vinyl-terminated dimethyl polysiloxane 30 wt%;

[0229] N-vinylpyrrolidone 39wt%;

[0230] 30 wt% isooctyl acrylate;

[0231] Photoinitiator Irgacure 2959 1wt%;

[0232] The preparation method of the above-mentioned vinyl-containing silicone rubber composite bulk material includes the following steps:

[0233] The corresponding amounts of vinyl-terminated dimethyl polysiloxane, N-vinylpyrrolidone, isooctyl acrylate, and photoinitiator Irgacure 2959 were placed in a thermostatic magnetic stirrer and stirred at 5000 rpm for 20 min to obtain a mixed solution. Then, the mixed solution was transferred to a polytetrafluoroethylene mold using a plastic dropper and cured under a 405nm / 100W ultraviolet lamp for 100 s to obtain a vinyl-containing silicone rubber composite body material.

[0234] Comparative Example 2

[0235] Compared to Example 8, the difference lies in the content of N-vinylpyrrolidone in the hydrophilic water solution. The hydrophilic water solution was adjusted to be hydrophilic and prepared from the following raw material components by mass percentage:

[0236] 3wt% N-vinylpyrrolidone

[0237] Photoinitiator Irgacure 819 0.1wt%;

[0238] Anhydrous ethanol 96.9 wt.

[0239] Other conditions and implementation steps are the same as in Example 8.

[0240] The surface water contact angle (WCA) of the silicone rubber material samples obtained in the above embodiments and comparative examples was tested, and the results are shown in Table 2 and the appendix. Figure 1-4 As shown.

[0241] Table 2

[0242] sample Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 WCA (°) 8.3 6.9 7.2 7.7 8.9 6.6 7.6 8.7 7.7 100.7 23.3

[0243] As can be seen from the examples and comparative examples, the surface water contact angle of the superhydrophilic antifouling silicone rubber composite material prepared by the present invention is less than 10°, thus achieving superhydrophilic properties.

[0244] Antifouling tests were conducted on the silicone rubber material samples of Example 2 and Comparative Examples 1-2 (taking Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) as examples); the anti-adhesion rate R results are shown in Table 3.

[0245] Table 3

[0246] sample Comparative Example 1 Comparative Example 2 Example 2 E. coli 0% 30.1% 72.2% S.aureus 0% 45.7% 75.7%

[0247] As can be seen from the antibacterial results of Example 2 and Comparative Examples 1-2, the superhydrophilic antifouling silicone rubber composite material prepared by the present invention has better antibacterial effect, i.e., antifouling performance.

[0248] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A superhydrophilic, antifouling silicone rubber composite material, characterized in that, The silicone rubber composite material comprises the following raw material components: Silicone rubber composite bulk material containing vinyl groups and aqueous solutions; The vinyl-containing silicone rubber composite body material comprises the following raw material components by mass percentage: 30wt%-40wt% of vinyl-containing silicone rubber; Modified monomers 29wt%-40wt%; Acrylic ester monomers 29wt%-40wt%; Photoinitiator 0.1wt%-5wt%; The aqueous solution comprises, by mass percentage, the following raw material components: Hydrophilic monomers 5wt%-90wt%; Photoinitiator 0.1wt%-5wt%; The remainder is solvent; The modified monomers include one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, or N-vinylimidazolone; The hydrophilic monomer includes one or more of N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-vinyl-N-methylacetamide, or N-vinylimidazolone.

2. The superhydrophilic antifouling silicone rubber composite material according to claim 1, characterized in that, The vinyl-containing silicone rubber includes one or more of the following: vinyl-terminated dimethyl polysiloxane, vinyl-terminated methyl vinyl polysiloxane, divinyl-terminated poly(dimethylsiloxane-co-diphenylsiloxane), vinyl-terminated methyl phenyl polysiloxane, vinyl-terminated dimethyl methyl vinyl (siloxane and polysiloxane), vinyl-terminated methyl phenyl polysiloxane, or vinyl-terminated dimethyl methyl-3,3,3-trifluoropropyl (siloxane and polysiloxane).

3. The superhydrophilic antifouling silicone rubber composite material according to claim 1 or 2, characterized in that, The acrylate monomers include one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, n-butyl methacrylate, or hydroxypropyl methacrylate.

4. The superhydrophilic antifouling silicone rubber composite material according to claim 1 or 2, characterized in that, The photoinitiator includes one or more of Irgacure 2959, Irgacure 184, Irgacure 907, Irgacure 1700, Darocure 1173, or Irgacure 819.

5. The superhydrophilic antifouling silicone rubber composite material according to claim 1 or 2, characterized in that, The solvent includes anhydrous ethanol.

6. The superhydrophilic antifouling silicone rubber composite material according to claim 1 or 2, characterized in that, The surface water contact angle of the silicone rubber composite material with a hydrophilic coating is 5-10°, preferably 5-9°.

7. A method for preparing a superhydrophilic antifouling silicone rubber composite material as described in claim 1, characterized in that, Includes the following steps: (1) A mixture is prepared by mixing vinyl-containing silicone rubber, modified monomer, acrylate monomer and photoinitiator, and the mixture is placed in a mold for photocuring to obtain a vinyl-containing silicone rubber composite body material; (2) A hydrophilic solution is obtained by mixing the hydrophilic monomer, diluent, photoinitiator and solvent; (3) The above-mentioned hydrophilic water solution is coated onto the silicone rubber composite body material containing vinyl groups, and then photocured to obtain a superhydrophilic antifouling silicone rubber composite material.

8. The preparation method according to claim 7, characterized in that, Step (3) can also involve immersing the vinyl-containing silicone rubber composite material in the hydrophilic solution of step (2) and then photocuring it to obtain a superhydrophilic antifouling silicone rubber composite material.

9. The preparation method according to claim 7 or 8, characterized in that, The light curing in step (1) includes ultraviolet light curing.

10. The application of the superhydrophilic antifouling silicone rubber composite material according to claims 1-6 or the superhydrophilic antifouling silicone rubber composite material prepared by the preparation method according to claims 7-9 in the field of medical devices; preferably, the field of medical devices includes one or more of artificial heart valves, artificial lenses, artificial meninges, artificial cochleas, artificial lung membranes, artificial fingers, artificial joints or artificial catheters.

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