A modified silicone rubber material for pessary and preparation method thereof
By injecting oxygen ions and silver ions on the surface of the silicone rubber material and loading the polymer film layer and modified hydroxyapatite, the problems of hydrophobicity, poor biocompatibility and lack of antibacterial properties of the silicone rubber material in pessary are solved, and higher biocompatibility, hydrophilicity, antibacteriality and wear resistance are achieved.
Patent Information
- Application Number
- CN202410953458.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-16
- Publication Date
- 2025-03-18
- Estimated Expiration
- 2044-07-16
AI Technical Summary
Existing silicone rubber materials are hydrophobic, poor biocompatibility and lack of antibacterial properties when used in pessary, resulting in a high risk of infection.
Oxygen ions and silver ions are injected on the surface of the silicone rubber by ion implantation to form an active silicone rubber material, and carboxymethyl chitosan and salicylic acid are loaded on its surface to form a polymer film layer. Finally, it is treated in a modified hydroxyapatite solution to improve the hydrophilicity, antibacteriality and wear resistance of the material.
The biocompatibility, hydrophilicity, antibacteriality and wear resistance of modified silicone rubber materials are significantly improved, and the risk of infection and the incidence of complications are reduced.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of medical material preparation, and in particular to a modified silicone rubber material for a pessary and a preparation method thereof. Background Art
[0002] A pessary is a medical device used to treat female uterine prolapse. Its manufacturing materials mainly include polyethylene, silicone rubber and polymer materials. Polyethylene is a widely used plastic material with the characteristics of non-toxicity, corrosion resistance and easy processing. In the production of pessaries, polyethylene is used to make support-type pessaries, such as ring-shaped pessaries; silicone rubber is a material with excellent biocompatibility, which is non-toxic and non-irritating to the human body, and has good elasticity and aging resistance. Therefore, silicone rubber is widely used to make pessaries, especially filled pessaries, such as horn-type and donut-type. These pessaries can better adapt to the needs of different patients and improve the treatment effect; in recent years, with the development of medical technology, some imported polymer materials have also been used to make pessaries. These materials have the advantages of high temperature resistance, corrosion resistance, long service life, etc., and meet relevant medical standards. They not only improve the comfort and durability of pessaries, but also reduce the risk of allergies and infections in patients.
[0003] Silicone rubber is widely used in the production of pessaries due to its unique biological inertness, easy processing and corrosion resistance. However, silicone rubber is highly hydrophobic and has poor compatibility with tissue cells. At the same time, silicone rubber material is not antibacterial, which makes it have a greater risk of infection.
[0004] Therefore, it is of great practical significance to improve the surface of silicone rubber to optimize the surface properties of the material and reduce the incidence of complications such as inflammation, infection, and capsular contracture. Summary of the invention
[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide a modified silicone rubber material for a pessary and a preparation method thereof.
[0006] In order to achieve the above object, the present invention adopts the following technical scheme:
[0007] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0008] S1, injecting oxygen ions and silver ions into the surface of silicone rubber by ion implantation to obtain an active silicone rubber material;
[0009] S2, adding the active silicone rubber material to the mixed solution, stirring, then taking out, washing, and drying to obtain a modified material; wherein the mixed solution is a mixed solution of carboxymethyl chitosan and salicylic acid;
[0010] S3, placing the modified material prepared in step S2 into a modified hydroxyapatite solution, adjusting the pH of the solution to 4-5, stirring at 40-60° C. for 8-16 hours, then taking out, washing, and drying to obtain a modified silicone rubber material.
[0011] Specifically, in step S1, the ion energy of the ion implantation is 10-20 keV, and the beam current density is 0.5-0.8 mA / cm 2 .
[0012] Specifically, in step S1, the implantation dose of oxygen ions is 1×10 15 ~1×10 17 ions / cm 2 The silver ion implantation dose is 1×10 15 ~1×10 17 ions / cm 2 .
[0013] Specifically, in step S2, the usage ratio of the active silicone rubber material and the mixed solution is 1 g: 10-15 mL.
[0014] Specifically, in step S2, the mass fraction of carboxymethyl chitosan in the mixed solution is 4-6%, and the mass fraction of salicylic acid is 2-4%.
[0015] Specifically, in step S3, the preparation method of the modified hydroxyapatite solution is as follows: nano-hydroxyapatite is dispersed in an ethanol aqueous solution, and then an epoxy silane coupling agent is added thereto, and stirred for 3-6 hours to obtain a modified hydroxyapatite solution.
[0016] Specifically, the mass ratio of nano-hydroxyapatite, ethanol aqueous solution and epoxy silane coupling agent is 3-5:100:0.5-1.
[0017] Specifically, the mass fraction of the ethanol aqueous solution is 60-80%.
[0018] Specifically, in step S3, the usage ratio of the modified material and the modified hydroxyapatite solution is 1 g: 5-10 mL.
[0019] The present invention also provides a modified silicone rubber material for a pessary prepared by the above preparation method.
[0020] Compared with the prior art, the present invention has the following beneficial effects:
[0021] (1) The present invention uses silicone rubber as a matrix material, first injects oxygen ions and silver ions into its surface to obtain an active silicone rubber material, then loads a polymer film layer, and finally loads hydroxyapatite. The prepared modified silicone rubber material has excellent biocompatibility, hydrophilicity, antibacterial and wear resistance.
[0022] (2) In the present invention, oxygen ions and silver ions are simultaneously injected into the silicone rubber surface. Compared with the single injection of silver ions, oxygen ions can further inhibit bacterial growth through oxidation reaction, help enhance the antibacterial effect of silver ions, and further improve the hydrophilicity of the material, which is beneficial to the subsequent loading of hydrophilic polymer membranes. In the present invention, carboxymethyl chitosan and salicylic acid are loaded on the surface of the active silicone rubber material to form a polymer membrane layer. Compared with the traditional loaded polydopamine membrane layer, the carboxymethyl chitosan and salicylic acid in the present invention have more excellent hydrophilicity and antibacterial properties, can form a stronger bond with the active silicone rubber material, and are convenient for the subsequent grafting of modified hydroxyapatite. In the present invention, by modifying hydroxyapatite, on the one hand, the water contact angle of hydroxyapatite is reduced, and on the other hand, the epoxy group reacts with the hydroxyl and carboxyl groups in the polymer membrane layer, thereby improving the loading stability of hydroxyapatite. By attaching the modified hydroxyapatite to the surface of the polymer membrane layer, the wear resistance of the modified silicone rubber material is improved.
[0023] (3) The modified silicone rubber material prepared in the present invention is used in the preparation process of medical devices such as pessaries, and has good practical value and application prospects. DETAILED DESCRIPTION
[0024] The present invention is further described in detail below through specific preferred embodiments, but the present invention is not limited to the following embodiments.
[0025] It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention were purchased through commercial channels.
[0026] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0027] S1. Preparation of active silicone rubber material
[0028] Oxygen ions and silver ions are implanted into the surface of silicone rubber by ion implantation to obtain active silicone rubber material.
[0029] In this step, the ion energy of the ion implantation is 10-20 keV, more preferably 12-16 keV; the beam current density is 0.5-0.8 mA / cm 2 , more preferably 0.6-0.7 mA / cm 2 .
[0030] In this step, the oxygen ion implantation dose is 1×10 15 ~1×10 17 ions / cm 2 In some embodiments of the present invention, for example, 1×10 15 ions / cm2 , 2×10 15 ions / cm 2 , 4×10 15 ions / cm 2 , 5×10 15 ions / cm 2 , 6×10 15 ions / cm 2 , 8×10 15 ions / cm 2 , 1×10 16 ions / cm 2 , 2×10 16 ions / cm 2 , 3×10 16 ions / cm 2 , 4×10 16 ions / cm 2 , 5×10 16 ions / cm 2 , 6×10 16 ions / cm 2 , 8×10 16 ions / cm 2 , 1×10 17 ions / cm 2 ; The silver ion implantation dose is 1×10 15 ~1×10 17 ions / cm 2 In some embodiments of the present invention, for example, 1×10 15 ions / cm 2 , 2×10 15 ions / cm 2 , 4×10 15 ions / cm 2 , 5×10 15 ions / cm 2 ,7×10 15 ions / cm 2 ,9×10 15 ions / cm 2 , 1×10 16 ions / cm 2 , 2×10 16 ions / cm 2 , 3×10 16 ions / cm 2 , 4×10 16 ions / cm 2 , 5×10 16 ions / cm2 , 6×10 16 ions / cm 2 , 8×10 16 ions / cm 2 , 1×10 17 ions / cm 2 ; but not limited to the listed values, other unlisted values within the numerical range are also applicable.
[0031] In this step, by injecting oxygen ions and silver ions into the silicone rubber surface at the same time, compared with the single injection of silver ions, the oxygen ions can further inhibit the growth of bacteria through oxidation reaction, help enhance the antibacterial effect of silver ions, and further improve the hydrophilicity of the material, which is beneficial to the subsequent loading of the hydrophilic polymer membrane.
[0032] S2. Preparation of modified materials
[0033] The active silicone rubber material is added into the mixed solution, stirred, then taken out, washed and dried to obtain the modified material; wherein the mixed solution is a mixed solution of carboxymethyl chitosan and salicylic acid.
[0034] In this step, the dosage ratio of the active silicone rubber material and the mixed solution is 1g:10-15mL. In some embodiments of the present invention, for example, 1g:10mL, 1g:11mL, 1g:12mL, 1g:13mL, 1g:14mL, 1g:15mL can be selected, but it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0035] In this step, the mass fraction of carboxymethyl chitosan in the mixed solution is 4-6%, for example, 4%, 5%, and 6% can be selected; the mass fraction of salicylic acid is 2-4%, for example, 2%, 3%, and 4% can be selected; but it is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0036] In this step, carboxymethyl chitosan and salicylic acid are loaded on the surface of the active silicone rubber material to form a polymer film layer. Compared with the traditional polydopamine loaded film layer, the carboxymethyl chitosan and salicylic acid in the present invention have more excellent hydrophilicity and antibacterial properties, can form a stronger bond with the active silicone rubber material, and are convenient for the subsequent grafting of modified hydroxyapatite.
[0037] S3. Preparation of modified silicone rubber material
[0038] The modified material prepared in step S2 is placed in a modified hydroxyapatite solution, the pH of the solution is adjusted to 4-5, stirred at 40-60° C. for 8-16 hours, then taken out, washed, and dried to obtain a modified silicone rubber material.
[0039] In this step, the preparation method of the modified hydroxyapatite solution is as follows: nano-hydroxyapatite is dispersed in an ethanol aqueous solution, and then an epoxy silane coupling agent is added thereto, and stirred for 3-6 hours to obtain a modified hydroxyapatite solution.
[0040] Specifically, the mass ratio of nano-hydroxyapatite, ethanol aqueous solution and epoxy silane coupling agent is 3-5:100:0.5-1, and more preferably 4-5:100:0.6-0.8.
[0041] Specifically, the mass fraction of the ethanol aqueous solution is 60-80%. In some embodiments of the present invention, for example, 60%, 65%, 70%, 75%, and 80% can be selected, but it is not limited to the listed values. Other unlisted values within the numerical range are also applicable.
[0042] The epoxy silane coupling agent used in the embodiment of the present invention is KH560.
[0043] In this step, the dosage ratio of the modified material and the modified hydroxyapatite solution is 1g:5-10mL, for example, 1g:5mL, 1g:6mL, 1g:7mL, 1g:8mL, 1g:9mL, 1g:10mL can be selected, but it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0044] In this step, by modifying hydroxyapatite, on the one hand, the water contact angle of hydroxyapatite is reduced, and on the other hand, the epoxy group reacts with the hydroxyl group and the carboxyl group in the polymer film layer to improve the load stability of hydroxyapatite, thereby improving the wear resistance of the modified silicone rubber material.
[0045] The present invention is further described below by means of specific examples. The particle size of the nano-hydroxyapatite used in the examples of the present invention is 40-60 nm.
[0046] Example 1
[0047] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0048] S1. Prepare the medical silicone rubber into a silicone rubber sheet with a thickness of 1 mm, and then inject a dose of 1×10 16 ions / cm 2 of oxygen ions and 1×10 16 ions / cm 2 The ion energy of the ion implantation is 15keV and the beam density is 0.6mA / cm 2 , obtaining an active silicone rubber material;
[0049] S2, adding 10g of active silicone rubber material into 100mL of mixed solution, stirring for 3h, then taking out, washing, and drying to obtain a modified material; wherein the mass fraction of carboxymethyl chitosan in the mixed solution is 5%, and the mass fraction of salicylic acid is 3%;
[0050] S3, placing 10 g of the modified material prepared in step S2 in 80 mL of modified hydroxyapatite solution, adjusting the pH of the solution to 4, stirring at 50° C. for 12 h, then taking out, washing, and drying to obtain a modified silicone rubber material;
[0051] The preparation method of the modified hydroxyapatite solution is as follows: 4 g of nano-hydroxyapatite is dispersed in 100 g of 75 wt% ethanol aqueous solution, and then 0.8 g of silane coupling agent KH560 is added thereto, and stirred for 5 hours to obtain the modified hydroxyapatite solution.
[0052] Example 2
[0053] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0054] S1. Prepare the medical silicone rubber into a silicone rubber sheet with a thickness of 1 mm, and then inject a dose of 1×10 17 ions / cm 2 of oxygen ions and 1×10 17 ions / cm 2 The ion energy of the ion implantation is 20keV and the beam density is 0.8mA / cm 2 , obtaining an active silicone rubber material;
[0055] S2, adding 10g of active silicone rubber material into 100mL of mixed solution, stirring for 3h, then taking out, washing, and drying to obtain a modified material; wherein the mass fraction of carboxymethyl chitosan in the mixed solution is 6%, and the mass fraction of salicylic acid is 4%;
[0056] S3, placing 10 g of the modified material prepared in step S2 in 100 mL of modified hydroxyapatite solution, adjusting the pH of the solution to 4, stirring at 60° C. for 8 h, then taking out, washing, and drying to obtain a modified silicone rubber material;
[0057] The preparation method of the modified hydroxyapatite solution is as follows: 5 g of nano-hydroxyapatite is dispersed in 100 g of 75 wt % ethanol aqueous solution, and then 1 g of silane coupling agent KH560 is added thereto, and stirred for 5 hours to obtain the modified hydroxyapatite solution.
[0058] Example 3
[0059] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0060] S1. Prepare the medical silicone rubber into a silicone rubber sheet with a thickness of 1 mm, and then inject a dose of 1×10 15 ions / cm 2 of oxygen ions and 1×10 15 ions / cm 2 The ion energy of the ion implantation is 10 keV and the beam density is 0.5 mA / cm 2 , obtaining an active silicone rubber material;
[0061] S2, adding 10g of active silicone rubber material to 120mL of the mixed solution, stirring for 3h, then taking out, washing, and drying to obtain a modified material; wherein the mass fraction of carboxymethyl chitosan in the mixed solution is 4%, and the mass fraction of salicylic acid is 2%;
[0062] S3, placing 10 g of the modified material prepared in step S2 in 50 mL of modified hydroxyapatite solution, adjusting the pH of the solution to 4, stirring at 60° C. for 8 h, then taking out, washing, and drying to obtain a modified silicone rubber material;
[0063] The preparation method of the modified hydroxyapatite solution is as follows: 3 g of nano-hydroxyapatite is dispersed in 100 g of 75 wt% ethanol aqueous solution, and then 0.5 g of silane coupling agent KH560 is added thereto, and stirred for 5 hours to obtain the modified hydroxyapatite solution.
[0064] Example 4
[0065] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0066] S1. Prepare the medical silicone rubber into a silicone rubber sheet with a thickness of 1 mm, and then inject a dose of 1×10 16 ions / cm 2 of oxygen ions and 1×10 15 ions / cm 2 The ion energy of the ion implantation is 20keV and the beam density is 0.8mA / cm 2 , obtaining an active silicone rubber material;
[0067] S2, adding 10g of active silicone rubber material into 150mL of mixed solution, stirring for 3h, then taking out, washing, and drying to obtain a modified material; wherein the mass fraction of carboxymethyl chitosan in the mixed solution is 5%, and the mass fraction of salicylic acid is 2%;
[0068] S3, placing 10 g of the modified material prepared in step S2 in 80 mL of modified hydroxyapatite solution, adjusting the pH of the solution to 4, stirring at 40° C. for 16 h, then taking out, washing, and drying to obtain a modified silicone rubber material;
[0069] The preparation method of the modified hydroxyapatite solution is as follows: 4 g of nano-hydroxyapatite is dispersed in 100 g of 75 wt% ethanol aqueous solution, and then 0.5 g of silane coupling agent KH560 is added thereto, and stirred for 5 hours to obtain the modified hydroxyapatite solution.
[0070] Comparative Example 1
[0071] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0072] S1. Prepare the medical silicone rubber into a silicone rubber sheet with a thickness of 1 mm, and then inject a dose of 1×10 16 ions / cm 2 The ion energy of the ion implantation is 15keV and the beam density is 0.6mA / cm 2 , obtaining an active silicone rubber material;
[0073] S2, adding 10g of active silicone rubber material into 100mL of mixed solution, stirring for 3h, then taking out, washing, and drying to obtain a modified material; wherein the mass fraction of carboxymethyl chitosan in the mixed solution is 5%, and the mass fraction of salicylic acid is 3%;
[0074] S3, placing 10 g of the modified material prepared in step S2 in 80 mL of modified hydroxyapatite solution, adjusting the pH of the solution to 4, stirring at 50° C. for 12 h, then taking out, washing, and drying to obtain a modified silicone rubber material;
[0075] The preparation method of the modified hydroxyapatite solution is as follows: 4 g of nano-hydroxyapatite is dispersed in 100 g of 75 wt% ethanol aqueous solution, and then 0.8 g of silane coupling agent KH560 is added thereto, and stirred for 5 hours to obtain the modified hydroxyapatite solution.
[0076] Compared with Example 1, Comparative Example 1 does not implant oxygen ions.
[0077] Comparative Example 2
[0078] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0079] S1. Prepare the medical silicone rubber into a silicone rubber sheet with a thickness of 1 mm, and then inject a dose of 1×10 16 ions / cm2 of oxygen ions and 1×10 16 ions / cm 2 The ion energy of the ion implantation is 15keV and the beam density is 0.6mA / cm 2 , obtaining an active silicone rubber material;
[0080] S2, adding 10g of active silicone rubber material to 100mL of 8wt% dopamine solution, stirring for 3h, then taking out, washing, and drying to obtain a modified material; wherein the preparation method of the dopamine solution is as follows: adding dopamine hydrochloride to a Tris-HCl buffer with a pH value of 8, and stirring evenly;
[0081] S3, placing 10 g of the modified material prepared in step S2 in 80 mL of modified hydroxyapatite solution, adjusting the pH of the solution to 4, stirring at 50° C. for 12 h, then taking out, washing, and drying to obtain a modified silicone rubber material;
[0082] The preparation method of the modified hydroxyapatite solution is as follows: 4 g of nano-hydroxyapatite is dispersed in 100 g of 75 wt% ethanol aqueous solution, and then 0.8 g of silane coupling agent KH560 is added thereto, and stirred for 5 hours to obtain the modified hydroxyapatite solution.
[0083] Compared with Example 1, Comparative Example 2 uses a dopamine solution instead of the mixed solution.
[0084] Comparative Example 3
[0085] A method for preparing a modified silicone rubber material for a pessary comprises the following steps:
[0086] S1. Prepare the medical silicone rubber into a silicone rubber sheet with a thickness of 1 mm, and then inject a dose of 1×10 16 ions / cm 2 of oxygen ions and 1×10 16 ions / cm 2 The ion energy of the ion implantation is 15keV and the beam density is 0.6mA / cm 2 , obtaining an active silicone rubber material;
[0087] S2, adding 10g of active silicone rubber material into 100mL of mixed solution, stirring for 3h, then taking out, washing, and drying to obtain a modified material; wherein the mass fraction of carboxymethyl chitosan in the mixed solution is 5%, and the mass fraction of salicylic acid is 3%;
[0088] S3, placing 10 g of the modified material prepared in step S2 in 80 mL of hydroxyapatite solution, adjusting the pH of the solution to 4, stirring at 50° C. for 12 h, then taking out, washing, and drying to obtain a modified silicone rubber material;
[0089] The preparation method of the hydroxyapatite solution is as follows: 4 g of nano-hydroxyapatite is dispersed in 100 g of 75 wt% ethanol aqueous solution to obtain the hydroxyapatite solution.
[0090] Compared with Example 1, in Comparative Example 3, no modification treatment was performed on the hydroxyapatite.
[0091] The modified silicone rubber materials prepared in Example 1 and Comparative Examples 1-3 were subjected to performance tests, as follows:
[0092] Hydrophilic performance test: Place the samples to be tested on the sample stage of the water contact angle analyzer, add 2 μL of deionized water on the surface, measure the contact angle between the water droplet and the surface, measure at 5 different positions of each sample, and take the average value of the measured water contact angles;
[0093] Antibacterial performance test: First prepare 2×10 5 cfu / ml bacterial suspension (Escherichia coli ATCC8099), then place the samples to be tested flat on sterile plates, take 0.4mL of bacterial suspension and drop it in the center of the material, spread it evenly, and cover it with a film; place it at 35℃ and relative humidity not less than 90% for 24h, then wash it, dilute it (PBS), count it after culture, and calculate the inhibition rate;
[0094] Friction coefficient test: The friction coefficient of medical devices and their surface coatings is measured using a rotational rheometer. The test piece is fixed on a glass plate and placed in the solution tank of the rotational rheometer. Deionized water is used as a lubricant. The plate is pressed against the sample surface with a positive pressure load of 0.6N. The rotor rotates unidirectionally at a speed of 1mm / s. The friction force is measured and the friction coefficient is calculated.
[0095] The test results are shown in the following table:
[0096] Water contact angle (°) Escherichia coli inhibition rate (%) Friction coefficient Example 1 19.6 99.5 0.085 Comparative Example 1 24.3 97.2 0.091 Comparative Example 2 28.4 94.7 0.088 Comparative Example 3 35.1 99.4 0.096
[0097] Wear resistance test: In water, a spherical indenter was used to conduct a unidirectional friction and wear test on the materials prepared in Example 1 and Comparative Examples 1-3 at a load of 2.16N to observe the wear. The test results show that after 100 friction tests, there was no obvious wear or damage on the surface of Example 1, and the surface morphology did not change significantly; in Comparative Example 1, no oxygen ions were injected, resulting in a weakened bonding force between the polymer film layer and the silicone rubber surface. After 43 frictions, the polymer film layer fell off; after 100 friction tests, there was no obvious wear or damage on the surface of Comparative Example 2, and the surface morphology did not change significantly; in Comparative Example 3, no modification was performed on hydroxyapatite, and the bonding force between hydroxyapatite and the polymer film layer was weak, and the mechanical properties were poor. After 29 frictions, it was damaged.
[0098] Finally, it should be noted that the above embodiments do not limit the present invention in any form. For those skilled in the art, some modifications and improvements can be made to the present invention. Therefore, any modification or improvement made without departing from the spirit of the present invention belongs to the scope of protection claimed in the present invention.
Claims
1. A method for preparing a modified silicone rubber material for a pessary, characterized in that: The steps include: S1, injecting oxygen ions and silver ions into the surface of silicone rubber by ion implantation to obtain an active silicone rubber material; S2, adding the active silicone rubber material to the mixed solution, stirring, then taking out, washing, and drying to obtain a modified material; The mixed solution is a mixed solution of carboxymethyl chitosan and salicylic acid; S3, placing the modified material prepared in step S2 in a modified hydroxyapatite solution, adjusting the pH of the solution to 4-5, stirring at 40-60° C. for 8-16 hours, then taking out, washing, and drying to obtain a modified silicone rubber material; Wherein, in step S3, the preparation method of the modified hydroxyapatite solution is as follows: nano-hydroxyapatite is dispersed in an ethanol aqueous solution, and then an epoxy silane coupling agent is added thereto, and stirred for 3-6 hours to obtain a modified hydroxyapatite solution; The mass ratio of nano-hydroxyapatite, ethanol aqueous solution and epoxy silane coupling agent is 3-5:100:0.5-1.
2. The preparation method according to claim 1, characterized in that: In step S1, the ion energy of ion implantation is 10-20keV and the beam current density is 0.5-0.8mA / cm 2 .
3. The preparation method according to claim 1, characterized in that: In step S1, the implantation dose of oxygen ions is 1×10 15 ~1×10 17 ions / cm 2 The silver ion implantation dose is 1×10 15 ~1×10 17 ions / cm 2 .
4. The preparation method according to claim 1, characterized in that: In step S2, the usage ratio of the active silicone rubber material and the mixed solution is 1 g: 10-15 mL.
5. The preparation method according to claim 1, characterized in that: In step S2, the mass fraction of carboxymethyl chitosan in the mixed solution is 4-6%, and the mass fraction of salicylic acid is 2-4%.
6. The preparation method according to claim 1, characterized in that: The mass fraction of the ethanol aqueous solution is 60-80%.
7. The preparation method according to claim 1, characterized in that: In step S3, the usage ratio of the modified material and the modified hydroxyapatite solution is 1 g: 5-10 mL.
8. The modified silicone rubber material for pessary prepared by the preparation method according to any one of claims 1 to 7.
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