Super-hydrophilic anti-fouling 3D printing silicone rubber valve composite material as well as preparation method and application thereof

Abstract

The invention discloses a super-hydrophilic anti-fouling 3D printing silicone rubber valve composite material as well as a preparation method and application thereof, and relates to the technical field of polymer composite materials. The super-hydrophilic anti-fouling 3D printing silicone rubber valve composite material comprises a 3D printing silicone rubber valve composite body material and a super-hydrophilic modified coating, and the 3D printing silicone rubber valve composite body material comprises the following components in parts by weight: 40-85 parts of a silicone rubber prepolymer, 40-85 parts of a cross-linking agent, 10-55 parts of an inorganic nano filler and 0.5-5 parts of a catalyst, the super-hydrophilic modified coating comprises the following components in parts by weight: 5-96 parts of deionized water, 5-80 parts of polyvinyl alcohol, 0.1-30 parts of citric acid and 0.1-10 parts of an antibacterial agent. The invention further provides a preparation method and application of the super-hydrophilic anti-fouling 3D printing silicone rubber valve composite material. The composite material provided by the invention has excellent super-hydrophilic and anti-fouling effects, and effectively solves the problem that the traditional silicone rubber valve is easy to cause thrombus and calcification.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically to a superhydrophilic and stain-resistant 3D-printed silicone rubber valve composite material, its preparation method, and its application. Background Technology

[0002] To date, the blood compatibility of existing minimally invasive implantable polymer heart valves (PHVs) remains poor. Platelets, cells, bacteria, viruses, and other contaminants easily adhere to their surfaces, forming "biofouling" that can induce thrombosis, inflammation, and calcification, leading to implantation failure. The root cause lies in the lack of effective anti-fouling and self-cleaning properties on the surface of PHVs.

[0003] Silicone rubber, such as polydimethylsiloxane (PDMS), is a common PHV material with good chemical stability and biocompatibility, and is widely used in the biomedical field. Based on previous research, 3D printing technology can be used to prepare porous PDMS materials with regular structures to simulate the fibrous structure of heart valves. However, many factors can affect the surface morphology and wettability of porous PDMS materials, and due to their high hydrophobicity, platelets, cells, and bacteria can still easily adhere to their surfaces. Therefore, constructing a superhydrophilic coating on the surface of 3D-printed porous PDMS materials is one of the important means to improve the surface's antifouling and self-cleaning properties. Summary of the Invention

[0004] To address the aforementioned shortcomings in the prior art, this invention provides a superhydrophilic and antifouling 3D-printed silicone rubber valve composite material, its preparation method, and its application. The aforementioned superhydrophilic and antifouling 3D-printed silicone rubber valve composite material exhibits excellent superhydrophilicity and antifouling properties, effectively solving the problems of high hydrophobicity, easy thrombosis, and calcification in traditional silicone rubber valves.

[0005] To achieve the above objectives, the technical solution adopted by the present invention to solve its technical problem is: to provide a superhydrophilic and antifouling 3D printed silicone rubber valve composite material, comprising a 3D printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D printed silicone rubber valve composite body material.

[0006] Furthermore, the aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 40-85 parts of silicone rubber prepolymer, 40-85 parts of crosslinking agent, 10-55 parts of inorganic nanofiller, and 0.5-5 parts of catalyst.

[0007] Furthermore, the aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 60 parts of silicone rubber prepolymer, 60 parts of crosslinking agent, 30 parts of inorganic nanofiller, and 3 parts of catalyst.

[0008] Furthermore, the silicone rubber prepolymer is at least one of vinyl silicone oil, divinyl silicone oil, methyl vinyl silicone oil, phenyl vinyl silicone oil, toluyl vinyl silicone oil, methyl phenyl vinyl silicone oil, and methyl vinyl trifluoropropyl silicone oil.

[0009] Furthermore, the crosslinking agent is terminal hydrogen silicone oil and / or polymethylhydrosiloxane.

[0010] Furthermore, the inorganic nanofiller is at least one of silicon dioxide, titanium dioxide, silicon carbide, calcium carbonate, carbon black, and graphene.

[0011] Furthermore, the catalyst is a platinum catalyst.

[0012] Furthermore, the catalyst is at least one of Dow Corning's RD27 platinum catalyst, Guangzhou Daxi Chemical Raw Materials Co., Ltd.'s DX-3080 platinum catalyst, and Dongguan Zhongxin Organosilicon Materials Co., Ltd.'s platinum catalyst.

[0013] Furthermore, the superhydrophilic modified coating comprises the following components in parts by weight: 5-96 parts deionized water, 5-80 parts polyvinyl alcohol, 0.1-30 parts citric acid, and 0.1-10 parts antibacterial agent.

[0014] Furthermore, the superhydrophilic modified coating comprises the following components in parts by weight: 50 parts deionized water, 40 parts polyvinyl alcohol, 15 parts citric acid, and 5 parts antibacterial agent.

[0015] Furthermore, the polyvinyl alcohol is PVA-1799.

[0016] Furthermore, the purity of citric acid is greater than 99%.

[0017] Furthermore, the antibacterial agent is silver nanoparticles and / or silver nanowires.

[0018] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. After uniformly mixing the silicone rubber prepolymer, crosslinking agent, inorganic nanofiller and catalyst, 3D printing is performed to obtain the 3D printed silicone rubber valve composite body material. S2. Mix polyvinyl alcohol, citric acid and antibacterial agent with deionized water to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2, and perform thermosetting crosslinking to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0019] Further, in step S1, the mixture is mixed in a three-roll mill for 5-120 min.

[0020] Further, in step S1, the mixture is mixed in a three-roll mill for 60 min.

[0021] Furthermore, in step S1, 3D printing is performed on an ink direct writing device.

[0022] Furthermore, in step S2, the mixture is mechanically dispersed in a water bath magnetic stirring pot for 30-240 min.

[0023] Furthermore, in step S2, the mixture is mechanically dispersed in a water bath magnetic stirring pot for 120 min.

[0024] Furthermore, in step S2, the soaking time is 3-120 s.

[0025] Furthermore, in step S2, the soaking time is 60 seconds.

[0026] Furthermore, in step S3, the thermosetting crosslinking time is 60-180 °C for 30-240 min.

[0027] Furthermore, in step S3, the thermosetting crosslinking time is 120 °C for 120 min.

[0028] The application of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material in the preparation of medical devices.

[0029] In summary, the present invention has the following beneficial effects: 1. Compared with traditional hydrophilic modification techniques, this invention uses 3D printing to prepare the physical morphology of a biomimetic valve, which has the designability of valve material structure and can meet the personalized structural needs of different patients. At the same time, the prepared superhydrophilic silicone rubber composite material has excellent superhydrophilicity and antifouling properties, which helps to reduce the accumulation of biofouling during valve operation and avoid increasing the burden on valve operation. Thus, it provides a new composite material and preparation method for biomedical materials such as silicone rubber artificial heart valves and their surface superhydrophilicity and antifouling modification.

[0030] 2. The superhydrophilic modified coating provided by this invention reduces the material's contact angle from a hydrophobic 153.8° to a superhydrophilic 0°, significantly improving hydrophilicity. Furthermore, it exhibits an anti-adhesion rate of over 99% against Escherichia coli and Staphylococcus aureus, effectively reducing the accumulation of biofouling (such as platelets and bacteria). Citric acid, as a green crosslinking agent, enhances the coating's stability, and combined with the broad-spectrum antibacterial properties of silver nanoparticles, extends the material's lifespan in biological environments. Attached Figure Description

[0031] Figure 1 Experimental results of water contact angle for 3D-printed silicone rubber flap composite material with superhydrophilic and antifouling properties; Figure 2The results show the water contact angle of the superhydrophobic silicone rubber flap composite material. Detailed Implementation

[0032] The principles and features of this invention are described below. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0033] Example 1 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0034] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 60 parts of silicone rubber prepolymer (the mass ratio of vinyl silicone oil, divinyl silicone oil, methyl vinyl silicone oil and phenyl vinyl silicone oil is 1:1:1:1), 60 parts of polymethylhydrosiloxane, 30 parts of inorganic nanofiller (the mass ratio of silica and graphene is 1:1), and 3 parts of RD27 platinum catalyst.

[0035] The above-mentioned superhydrophilic modified coating comprises the following components by weight: 50 parts deionized water, 40 parts PVA-1799, 15 parts citric acid with a purity greater than 99%, and 5 parts silver nanoparticles.

[0036] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. After mixing vinyl silicone oil, divinyl silicone oil, methyl vinyl silicone oil and phenyl vinyl silicone oil, polymethylhydrosiloxane, silica, graphene and Dow Corning's RD27 platinum catalyst in a three-roll mill for 60 min, the mixture is 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanoparticles are mechanically dispersed with deionized water in a water bath magnetic stirring pot for 120 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 60 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 120 ℃ and the time is 120 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0037] Example 2 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0038] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 40 parts of silicone rubber prepolymer (methyl vinyl silicone oil, toluene vinyl silicone oil, methyl phenyl vinyl silicone oil and methyl vinyl trifluoropropyl silicone oil in a mass ratio of 1:1:1:1), 40 parts of terminal hydrogen silicone oil, 10 parts of inorganic nanofiller (silicon dioxide, titanium dioxide and silicon carbide in a mass ratio of 1:1:1), and 0.5 parts of DX-3080 platinum catalyst.

[0039] The above-mentioned superhydrophilic modified coating comprises the following components by weight: 5 parts deionized water, 5 parts PVA-1799, 0.1 parts citric acid with a purity greater than 99%, and 0.1 parts silver nanowires.

[0040] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. Methyl vinyl silicone oil, toluene vinyl silicone oil, methyl phenyl vinyl silicone oil, methyl vinyl trifluoropropyl silicone oil, terminal hydrogen silicone oil, silicon dioxide, titanium dioxide, silicon carbide and DX-3080 platinum catalyst from Guangzhou Daxi Chemical Raw Materials Co., Ltd. are mixed in a three-roll mill for 5 min and then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanoparticles are mechanically dispersed with deionized water in a water bath magnetic stirring pot for 30 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 3 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 60 ℃ and the time is 30 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0041] Example 3 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0042] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components in parts by weight: 85 parts of silicone rubber prepolymer (a mass ratio of vinyl silicone oil, divinyl silicone oil, methyl vinyl silicone oil, phenyl vinyl silicone oil, toluyl vinyl silicone oil, methyl phenyl vinyl silicone oil, and methyl vinyl trifluoropropyl silicone oil of 1:1:1:1:1:1:1), 85 parts of crosslinking agent (a mass ratio of polymethylhydrosiloxane and terminal hydrogen silicone oil of 1:1), 55 parts of inorganic nanofiller (a mass ratio of silicon dioxide, titanium dioxide, silicon carbide, calcium carbonate, carbon black, and graphene of 1:1:1:1:1:1), and 5 parts of platinum catalyst (a mass ratio of RD27 platinum catalyst and DX-3080 platinum catalyst of 1:1).

[0043] The above-mentioned superhydrophilic modified coating comprises the following components in parts by weight: 96 parts deionized water, 80 parts PVA-1799, 30 parts citric acid with a purity greater than 99%, and 10 parts silver nanoparticles.

[0044] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. Vinyl silicone oil, divinyl silicone oil, methyl vinyl silicone oil, phenyl vinyl silicone oil, toluyl vinyl silicone oil, methyl phenyl vinyl silicone oil, methyl vinyl trifluoropropyl silicone oil, polymethylhydrosiloxane, terminal hydrogen silicone oil, silicon dioxide, titanium dioxide, silicon carbide, calcium carbonate, carbon black, graphene, Dow Corning's RD27 platinum catalyst and DX-3080 platinum catalyst are mixed in a three-roll mill for 120 min, and then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanoparticles are mechanically dispersed with deionized water in a water bath magnetic stirring pot for 240 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 120 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 180 ℃ and the time is 240 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0045] Example 4 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0046] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 60 parts of silicone rubber prepolymer (methyl vinyl silicone oil, phenyl vinyl silicone oil and toluene vinyl silicone oil in a mass ratio of 1:1:1), 60 parts of polymethylhydrosiloxane, 30 parts of inorganic nanofiller (silicon carbide, calcium carbonate and carbon black in a mass ratio of 1:1), and 3 parts of RD27 platinum catalyst.

[0047] The above-mentioned superhydrophilic modified coating comprises the following components in parts by weight: 50 parts deionized water, 40 parts PVA-1799, 15 parts citric acid with a purity greater than 99%, and 5 parts silver nanowires.

[0048] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. Methyl vinyl silicone oil, phenyl vinyl silicone oil, toluene vinyl silicone oil, polymethylhydrosiloxane, silicon carbide, calcium carbonate, carbon black and Dow Corning's RD27 platinum catalyst are mixed in a three-roll mill for 60 min and then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanowires are mechanically dispersed with deionized water in a water bath with magnetic stirring for 120 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 60 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 120 ℃ and the time is 120 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0049] Example 5 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0050] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 60 parts of silicone rubber prepolymer (the mass ratio of divinyl silicone oil and methylvinyl silicone oil is 1:1), 60 parts of terminal hydrogen silicone oil, 30 parts of graphene, and 3 parts of RD27 platinum catalyst.

[0051] The above-mentioned superhydrophilic modified coating comprises the following components in parts by weight: 50 parts deionized water, 40 parts PVA-1799, 15 parts citric acid with a purity greater than 99%, and 5 parts silver nanowires.

[0052] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. Divinyl silicone oil, methyl vinyl silicone oil, terminal hydrogen silicone oil, silicon carbide, graphene and Dow Corning's RD27 platinum catalyst are mixed in a three-roll mill for 60 min and then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanowires are mechanically dispersed with deionized water in a water bath with magnetic stirring for 120 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 60 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 120 ℃ and the time is 120 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0053] Example 6 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0054] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 60 parts of silicone rubber prepolymer (the mass ratio of vinyl silicone oil, toluene vinyl silicone oil and methyl phenyl vinyl silicone oil is 1:1:1), 60 parts of terminal hydrogen silicone oil, 30 parts of calcium carbonate, and 3 parts of platinum catalyst from Dongguan Zhongxin Organosilicon Materials Co., Ltd.

[0055] The above-mentioned superhydrophilic modified coating comprises the following components in parts by weight: 50 parts deionized water, 40 parts PVA-1799, 15 parts citric acid with a purity greater than 99%, and 5 parts silver nanowires.

[0056] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. After mixing vinyl silicone oil, toluene vinyl silicone oil, terminal hydrogen silicone oil, calcium carbonate and platinum catalyst from Dongguan Zhongxin Organosilicon Materials Co., Ltd. in a three-roll mill for 60 min, the mixture is then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanowires are mechanically dispersed with deionized water in a water bath with magnetic stirring for 120 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 60 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 120 ℃ and the time is 120 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0057] Example 7 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0058] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 60 parts of silicone rubber prepolymer (the mass ratio of vinyl silicone oil, methyl vinyl silicone oil, phenyl vinyl silicone oil, toluene vinyl silicone oil and methyl vinyl trifluoropropyl silicone oil is 1:1:1:1:1), 60 parts of polymethylhydrosiloxane, 30 parts of inorganic nanofiller (the mass ratio of titanium dioxide, silicon carbide and carbon black is 1:1:1), and 3 parts of DX-3080 platinum catalyst.

[0059] The above-mentioned superhydrophilic modified coating comprises the following components in parts by weight: 50 parts deionized water, 40 parts PVA-1799, 15 parts citric acid with a purity greater than 99%, and 5 parts silver nanowires.

[0060] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. Vinyl silicone oil, methyl vinyl silicone oil, phenyl vinyl silicone oil, toluene vinyl silicone oil, methyl vinyl trifluoropropyl silicone oil, polymethylhydrosiloxane, titanium dioxide, silicon carbide, carbon black, and DX-3080 platinum catalyst from Guangzhou Daxi Chemical Raw Materials Co., Ltd. were mixed in a three-roll mill for 60 min and then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanowires are mechanically dispersed with deionized water in a water bath with magnetic stirring for 120 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 60 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 120 ℃ and the time is 120 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0061] Example 8 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0062] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 60 parts of silicone rubber prepolymer (the mass ratio of vinyl silicone oil, phenyl vinyl silicone oil and toluene vinyl silicone oil is 1:1:1), 60 parts of polymethylhydrosiloxane, 30 parts of inorganic nanofiller (the mass ratio of silica and calcium carbonate is 1:1), and 3 parts of DX-3080 platinum catalyst.

[0063] The above-mentioned superhydrophilic modified coating comprises the following components by weight: 50 parts deionized water, 40 parts PVA-1799, 15 parts citric acid with a purity greater than 99%, and 5 parts silver nanoparticles.

[0064] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. After mixing vinyl silicone oil, phenyl vinyl silicone oil, toluene vinyl silicone oil, polymethylhydrosiloxane, silica, calcium carbonate and DX-3080 platinum catalyst from Guangzhou Daxi Chemical Raw Materials Co., Ltd. in a three-roll mill for 60 min, the mixture is then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanoparticles are mechanically dispersed with deionized water in a water bath magnetic stirring pot for 120 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 60 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 120 ℃ and the time is 120 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0065] Example 9 A superhydrophilic and antifouling 3D-printed silicone rubber valve composite material includes a 3D-printed silicone rubber valve composite body material and a superhydrophilic modified coating, wherein the superhydrophilic modified coating is disposed on the surface of the 3D-printed silicone rubber valve composite body material.

[0066] The aforementioned 3D printed silicone rubber valve composite body material comprises the following components by weight: 60 parts of silicone rubber prepolymer (the mass ratio of divinyl silicone oil, methyl vinyl silicone oil, methyl phenyl vinyl silicone oil and methyl vinyl trifluoropropyl silicone oil is 1:1:1:1), 60 parts of terminal hydrogen silicone oil, 30 parts of inorganic nanofiller (the mass ratio of silicon dioxide and graphene is 1:1), and 3 parts of RD27 platinum catalyst.

[0067] The above-mentioned superhydrophilic modified coating comprises the following components by weight: 50 parts deionized water, 40 parts PVA-1799, 15 parts citric acid with a purity greater than 99%, and 5 parts silver nanoparticles.

[0068] The preparation method of the above-mentioned superhydrophilic and antifouling 3D printed silicone rubber valve composite material includes the following steps: S1. Divinyl silicone oil, methyl vinyl silicone oil, methyl phenyl vinyl silicone oil, methyl vinyl trifluoropropyl silicone oil, polymethylhydrosiloxane, silica, graphene and Dow Corning's RD27 platinum catalyst are mixed in a three-roll mill for 60 min and then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber valve composite body material. S2. PVA-1799, citric acid with a purity greater than 99%, and silver nanoparticles are mechanically dispersed with deionized water in a water bath magnetic stirring pot for 120 min to obtain a superhydrophilic modified coating solution. S3. Immerse the 3D printed silicone rubber valve composite material obtained in step S1 in the superhydrophilic modified coating solution obtained in step S2 for 60 s to perform thermosetting crosslinking. The thermosetting crosslinking time is 120 ℃ and the time is 120 min to obtain a superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0069] Comparative Example 1 Superhydrophobic 3D printed silicone rubber valve composite material, including only the 3D printed silicone rubber valve composite body material.

[0070] The aforementioned superhydrophobic 3D printed silicone rubber flap composite material comprises the following components: 20g of Dow Corning 184A, 2g of Dow Corning 184B, and 4g of nano-silica.

[0071] The above-mentioned method for preparing superhydrophobic 3D printed silicone rubber flap composite material includes the following steps: S1. Dow Corning 184A, Dow Corning 184B and nano silica are mixed in a three-roll mill for 60 min and then 3D printed on an ink direct writing device to obtain a 3D printed silicone rubber flap composite body material. S2. The 3D printed silicone rubber valve composite material obtained in step S1 is subjected to thermosetting crosslinking at 120 °C for 120 min to obtain a superhydrophobic 3D printed silicone rubber valve composite material.

[0072] Experimental Example 1 The superhydrophilic and antifouling 3D-printed silicone rubber valve composite materials prepared in Examples 1-9 and the superhydrophobic silicone rubber valve composite material prepared in Comparative Example 1 were subjected to surface water contact angle (WCA) tests to determine their surface hydrophilicity / hydrophobicity wettability changes. The WCA test results of Examples 1-9 and Comparative Example 1 are shown in Table 1. The contact angle test results of Example 8 are as follows: Figure 1 As shown, the contact angle experimental results of Comparative Example 1 are as follows: Figure 2 As shown.

[0073] Table 1 Contact Angle Test Results

[0074] From Table 1 and Figure 1-2 It can be seen that the water contact angle of Comparative Example 1 is 153.8°, which is superhydrophobic and has a large water contact angle; the water contact angles of Examples 1-9 are all 0°, which is superhydrophilic. This shows that the method described in the invention can effectively prepare superhydrophilic and antifouling 3D printed silicone rubber valve composite material.

[0075] Experimental Example 2 The superhydrophilic and antifouling 3D-printed silicone rubber valve composite materials prepared in Examples 2 and 5 were compared with the superhydrophobic silicone rubber valve composite material prepared in Comparative Example 1. Antifouling experiments were conducted using Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) as examples. The anti-adhesion rate results are shown in Table 2.

[0076] Table 2 Anti-adhesion rate results

[0077] As shown in Table 2, the superhydrophilic and antifouling 3D-printed silicone rubber flap composite material prepared by this invention has better antibacterial effect, i.e., antifouling performance.

[0078] 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 super-hydrophilic, stain repellent 3D printed silicone rubber valve composite material, characterized in that, The super-hydrophilic modified coating is arranged on the surface of the 3D-printed silicone rubber valve composite body material.

2. The super-hydrophilic anti-fouling 3D-printed silicone rubber valve composite of claim 1, wherein, The 3D-printed silicone rubber valve composite body material comprises the following components by weight: 40-85 parts of a silicone rubber prepolymer, 40-85 parts of a crosslinking agent, 10-55 parts of inorganic nano-filler, and 0.5-5 parts of a catalyst.

3. The super-hydrophilic anti-fouling 3D-printed silicone rubber valve composite of claim 2, wherein, The silicone rubber prepolymer is at least one of vinyl silicone oil, divinyl silicone oil, methyl vinyl silicone oil, phenyl vinyl silicone oil, tolyl vinyl silicone oil, methyl phenyl vinyl silicone oil, and methyl vinyl trifluoropropyl silicone oil.

4. The super-hydrophilic anti-fouling 3D-printed silicone rubber valve composite of claim 2, wherein, The crosslinking agent is terminal hydrogen silicone oil or / and polymethyl hydrogen siloxane.

5. The super-hydrophilic anti-fouling 3D-printed silicone rubber valve composite of claim 2, wherein, The inorganic nano-filler is at least one of silicon dioxide, titanium dioxide, silicon carbide, calcium carbonate, carbon black, and graphene.

6. The super-hydrophilic anti-fouling 3D-printed silicone rubber valve composite of claim 2, wherein, The catalyst is a platinum-gold catalyst.

7. The super-hydrophilic anti-fouling 3D-printed silicone rubber valve composite of claim 1, wherein, The super-hydrophilic modified coating comprises the following components by weight: 5-96 parts of deionized water, 5-80 parts of polyvinyl alcohol, 0.1-30 parts of citric acid, and 0.1-10 parts of an antibacterial agent.

8. The super-hydrophilic anti-fouling 3D-printed silicone rubber valve composite of claim 7, wherein, The antibacterial agent is silver nanoparticles or silver nanowires.

9. The method of making a super-hydrophilic anti-fouling 3D-printed silicone rubber valve composite of any one of claims 1-8, characterized in that, The method comprises the following steps: S1, uniformly mixing a silicone rubber prepolymer, a crosslinking agent, inorganic nano-filler, and a catalyst, and then 3D printing to obtain a 3D-printed silicone rubber valve composite body material; S2, uniformly mixing polyvinyl alcohol, citric acid, and an antibacterial agent with deionized water to obtain a super-hydrophilic modified coating solution; S3, soaking the 3D-printed silicone rubber valve composite body material obtained in step S1 in the super-hydrophilic modified coating solution obtained in step S2, and performing heat-solid crosslinking to obtain a super-hydrophilic and stain-resistant 3D-printed silicone rubber valve composite material.

10. Use of the super-hydrophilic and stain-resistant 3D-printed silicone rubber valve composite material of claim 1 in the preparation of a medical device.

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