Silicone rubber plate for blending bone cement and preparation process of silicone rubber plate

Abstract

The invention discloses a silicone rubber plate for blending bone cement and a preparation process thereof, and relates to the technical field of silicone rubber plates, the preparation process comprises the following steps: adding silicone rubber, fluorinated silicone rubber and a double vulcanizing agent into a kneading machine, adjusting roller spacing, preparing into tablets, and vulcanizing to obtain a silicone rubber raw sheet; cutting and forming a silicone rubber raw sheet, and ultrasonically cleaning in ethanol for later use; the preparation method comprises the following steps: treating the surface of a cleaned raw silicon rubber sheet by using a nanosecond laser and performing laser drilling treatment by using a picosecond laser in sequence, then preparing nano silicon dioxide through hydrolytic condensation of ethyl silicate to fill holes, cleaning a drilling area on the surface by using the picosecond laser, and finally performing hydrophobic modification by using hexamethyldisilazane to obtain the super-hydrophobic silicon rubber plate. The preparation method comprises the following steps: carrying out sulfydryl modification on the surface of a super-hydrophobic silicone rubber plate, grafting ammonium bromide on the surface of the super-hydrophobic silicone rubber plate through an ultraviolet sulfydryl olefin reaction, grafting through an L-proline reaction, and finally absorbing nitric oxide to be saturated to obtain the silicone rubber plate for blending the bone cement.

Description

Technical Field

[0001] The invention relates to the technical field of silicone rubber plates, in particular to a silicone rubber plate for mixing bone cement and a preparation process thereof. Background Art

[0002] In the prior art, the materials used in traditional bone cement mixing often lack sufficient high-temperature friction resistance, resulting in the heat generated during the mixing process causing serious wear on the materials. This wear not only affects the physical properties of the materials, but may also reduce mixing efficiency and increase surgical risks. In addition, the hydrophobic properties of existing materials are limited, which can easily cause bone cement to adhere during mixing, increasing the complexity of cleaning and maintenance.

[0003] At the same time, the antibacterial properties of traditional materials are insufficient, which increases the risk of postoperative infection and poses a hidden danger to patient safety. These shortcomings urgently need to be addressed through the development and improvement of new materials to improve the overall efficiency and safety of the bone cement mixing process.

[0004] Therefore, it is of great significance to invent a silicone rubber sheet for bone cement mixing and a preparation process thereof. Summary of the invention

[0005] The purpose of the present invention is to provide a silicone rubber sheet for mixing bone cement and a preparation process thereof, so as to solve the problems raised in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A preparation process of a silicone rubber sheet for mixing bone cement comprises the following steps: S1: preheating a kneading machine, adjusting the roller distance, adding silicone rubber, mixing for 5-6 minutes, reducing the roller distance, adding polytetrafluoroethylene, mixing for 10-15 minutes, adding fluorosilicone rubber and a disulfide vulcanizer in sequence, mixing for 10-15 minutes, increasing the roller distance, making tablets, standing at room temperature, placing the tablets on a flat vulcanizer for vulcanization, and obtaining silicone rubber original sheets;

[0008] During the preparation of the silicone rubber sheet, the proportions of the components by mass include: 90-100 parts of silicone rubber, 5-10 parts of polytetrafluoroethylene, 5-10 parts of fluorosilicone rubber, and 1.6-2 parts of disulfide;

[0009] The adjusting roller distance is 4-6mm, the reducing roller distance is 2-3mm, and the expanding roller distance is 3-4mm;

[0010] The preheating temperature is 30-35°C, the vulcanization temperature is 175-180°C, and the time is 10-12 minutes;

[0011] S2: Cut the silicone rubber sheet into pieces, clean it ultrasonically in ethanol, and set it aside;

[0012] The cutting specifications include: length 155-160mm, width 100-105mm, thickness 3-4mm;

[0013] S3: After the surface of the cleaned silicone rubber original sheet is treated with a nanosecond laser, the surface is laser drilled with a picosecond laser, and ultrasonic cleaning is performed with ethanol to obtain a silicone rubber rough plate; the silicone rubber rough plate is immersed in an 8-10wt% polydiallyldimethylammonium chloride solution, ultrasonically treated, taken out and dried in a 50-55°C environment for 2-2.5h, and then immersed in an ethyl silicate solution, ultrasonically treated, and allowed to stand at room temperature in the solution for 48-60h, vacuum dried, and the surface of the silicone rubber rough plate except the drilling area is cleaned with a picosecond laser, and finally immersed in a 20-25wt% hexamethyldisilazane solution, heated to 35-45°C for reaction for 2-3h, and vacuum dried to obtain a superhydrophobic silicone rubber plate;

[0014] The nanosecond laser processing parameters include: wavelength 1064nm, repetition rate 100kHz, spot overlap 70%, scanning rate 1475mm / s, spot diameter 50μm, laser energy density 12.5J / cm 2 , pulse width 340ns;

[0015] The picosecond laser drilling processing parameters include: wavelength 542nm, repetition rate 100kHz, point overlap 75%, scanning rate 500mm / s, spot diameter 20μm, laser energy density 14.3J / cm 2 , pulse width 12ps;

[0016] The laser drilling process is a periodic array structure surface treatment, and its parameters include: hole radius 100 μm, hole spacing 100-258 μm, hole depth 400 μm;

[0017] The ethyl silicate solution is composed of deionized water, anhydrous ethanol, ammonium hydroxide and ethyl silicate in a molar ratio of 0.5:1:1:3.5;

[0018] The picosecond laser surface cleaning parameters include: wavelength 542nm, repetition rate 100kHz, spot overlap 70%, scanning rate 590mm / s, spot diameter 20μm, laser energy density 6.0J / cm 2 , pulse width 12ps;

[0019] S4: Add 2-(dimethylamino)ethyl acrylate and 1-bromooctane to acetonitrile, stir evenly, heat to 45-50°C and react for 3 days to obtain ammonium bromide;

[0020] In the preparation of the ammonium bromide, the molar ratio of 2-(dimethylamino)ethyl acrylate:1-bromooctane is 1:1;

[0021] S5: Immerse the super-hydrophobic silicone rubber sheet in a methanol solution containing 10-15wt% 3-mercaptopropyltrimethoxysilane and 1% W / V potassium hydroxide, heat to 50-55°C for reaction for 6-6.5h, immerse in methanol, ultrasonicate, and finally immerse in dichloromethane and stir for 3-3.5h to obtain a mercapto-modified silicone rubber sheet; under a nitrogen atmosphere, ammonium bromide, 2-methyl-2-acrylic acid-2-(2-methoxyethoxy)ethyl ester, 2,2-dimethoxy-2- Phenyl acetophenone is added to methanol, stirred evenly, and dripped onto the surface of the thiol-modified silicone rubber sheet, irradiated with ultraviolet light for 1-1.5 hours, washed with methanol and deionized water, and vacuum dried to obtain an ammonium bromide-modified silicone rubber sheet; the ammonium bromide-modified silicone rubber sheet is immersed in an 8-12wt% L-proline solution, stirred at room temperature for 12-14 hours, ventilated with nitrogen for 30-45 minutes, and then nitric oxide is introduced to saturation, and the solution is kept warm for absorption for 1-1.5 hours to obtain a silicone rubber sheet for bone cement blending.

[0022] In the preparation process of the ammonium bromide-modified silicone rubber sheet, the molar ratio of ammonium bromide:2-methyl-2-acrylate-2-(2-methoxyethoxy)ethyl ester is 1:1;

[0023] The L-proline solution was made alkaline using 0.01 M sodium hydroxide.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. In order to improve the high-temperature friction resistance of the silicone rubber sheet during the mixing process of bone cement, the present invention uses fluorosilicone rubber as a compatibilizer to improve the compatibility of silicone rubber and polytetrafluoroethylene, thereby greatly improving the high-temperature friction stability of the silicone rubber sheet while maintaining the original mechanical properties. The introduction of polytetrafluoroethylene can improve the high-temperature friction stability of the rubber and reduce the high-temperature friction coefficient of the rubber. During the high-temperature friction and wear process, polytetrafluoroethylene and rubber abrasive particles adhere a molten layer on the rubber surface to reduce friction resistance. It exhibits excellent wear resistance at high temperatures, and the molten layer formed by friction can prevent direct contact between air and the surface rubber, inhibit the high-temperature oxidation reaction of the rubber surface, thereby reducing the friction loss of the silicone rubber sheet caused by the high temperature generated during the mixing of bone cement, and reducing the impact on the performance of bone cement during the application process.

[0026] 2. The present invention plans to further enhance the friction resistance and antibacterial properties of the silicone rubber sheet on the basis of the excellent original silicone rubber sheet. After irradiating the silicone rubber surface with a nanosecond laser, a periodic circular hole array with a depth of 400 μm is created with a picosecond laser, and the aperture and hole spacing of the periodic circular hole array are adjusted to achieve the best hydrophobic performance, thereby avoiding the adhesion of bone cement on the surface of the silicone rubber sheet during stirring. Then, silica particles are filled with ethyl silicate by direct hydrolysis. After laser cleaning and silanization modification, a surface composed of soft silicone rubber and hard silica regions is prepared to obtain a super hydrophobic silicone rubber sheet with excellent friction resistance.

[0027] 3. Finally, the present invention prepares a silicone rubber sheet having a quaternary ammonium ion liquid coating with antibacterial and antifouling properties due to the synergistic effect of interleukin and released nitric oxide by grafting ammonium bromide and 2-methyl-2-acrylate-2-(2-methoxyethoxy)ethyl ester on the surface of a super-hydrophobic silicone rubber sheet and then introducing proline- through anion exchange between Br and proline to adsorb nitric oxide. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] In the following embodiments, silicone rubber specification: NE-5150, purchased from Dongjue Silicone (Nanjing) Co., Ltd.; fluorosilicone rubber specification: FSR8460-U, purchased from Dongguan Ningdao Rubber Co., Ltd.; disulfide vulcanizing agent specification: TC-14 di-2-5 vulcanizing agent, purchased from Dongguan Tengqi Rubber and Plastic Technology Co., Ltd.; polytetrafluoroethylene specification: MP1000, purchased from DuPont, USA; the remaining raw materials are commercially available.

[0030] In the following examples, the preparation process of ammonium bromide includes the following steps: 10 mmol 2-(dimethylamino)ethyl acrylate and 10 mmol 1-bromooctane are added to 20 mL acetonitrile, stirred evenly, and heated to 45° C. for reaction for 3 days to obtain ammonium bromide.

[0031] Embodiment 1: A process for preparing a silicone rubber sheet for mixing bone cement, comprising the following steps: S1: preheating a kneading machine at 30°C for 5 minutes, adjusting the roller distance to 4mm, adding 100 parts of silicone rubber, mixing for 5 minutes, reducing the roller distance by 2mm, adding 5 parts of polytetrafluoroethylene, mixing for 10 minutes, adding 5 parts of fluorosilicone rubber and 1.6 parts of disulfide in sequence, mixing for 10 minutes, increasing the roller distance by 3mm, making tablets, standing at room temperature, placing the tablets on a flat vulcanizer and vulcanizing at 175°C for 10 minutes, and obtaining silicone rubber original sheets;

[0032] S2: Cut the original silicone rubber sheet into pieces with a length of 157 mm, a width of 102 mm, and a thickness of 3 mm, and clean them ultrasonically in ethanol for later use;

[0033] S3: After the surface of the cleaned silicone rubber original sheet is treated with a nanosecond laser, the surface is laser drilled with a picosecond laser, and ultrasonic cleaning is performed with ethanol to obtain a silicone rubber rough plate; the silicone rubber rough plate is immersed in an 8wt% polydiallyldimethylammonium chloride solution, ultrasonically treated, taken out and dried in a 50°C environment for 2h, and then immersed in an ethyl silicate solution, ultrasonically treated, and allowed to stand in the solution at room temperature for 48h, vacuum dried, and the surface of the silicone rubber rough plate except the drilling area is cleaned with a picosecond laser, and finally immersed in a 20wt% hexamethyldisilazane solution, heated to 35°C for reaction for 2h, and vacuum dried to obtain a super-hydrophobic silicone rubber plate; the laser drilling treatment is a periodic array structure surface treatment, and its parameters include: hole radius 100μm, hole spacing 258μm, and hole depth 400μm;

[0034] S4: Immerse the super-hydrophobic silicone rubber sheet in a methanol solution containing 10wt% 3-mercaptopropyltrimethoxysilane and 1% W / V potassium hydroxide, heat to 50°C for reaction for 6h, then immerse in methanol, ultrasonically treat, and finally immerse in dichloromethane and stir for 3h to obtain a thiol-modified silicone rubber sheet; under a nitrogen atmosphere, add 0.3mmol ammonium bromide, 0.3mmol 2-methyl-2-acrylic acid-2-(2-methoxyethoxy)ethyl ester, and 24mg 2,2-dimethoxy-2-phenylacetophenone to methanol, stir evenly, and drop them on the surface of the thiol-modified silicone rubber sheet, irradiate with ultraviolet light for 1h, wash with methanol and deionized water, and vacuum dry to obtain an ammonium bromide-modified silicone rubber sheet; immerse the ammonium bromide-modified silicone rubber sheet in an 8wt% L-proline solution, stir at room temperature for 12h, ventilate with nitrogen for 30min, then pass nitric oxide to saturation, keep warm and absorb for 1h to obtain a silicone rubber sheet for bone cement blending.

[0035] Embodiment 2: A preparation process of a silicone rubber sheet for mixing bone cement: comprising the following steps: S3: treating the surface of the cleaned silicone rubber original sheet with a nanosecond laser, then laser drilling the surface with a picosecond laser, and ultrasonic cleaning with ethanol to obtain a silicone rubber rough sheet; immersing the silicone rubber rough sheet in an 8wt% polydiallyldimethylammonium chloride solution, ultrasonically treating it, taking it out and drying it in a 50°C environment for 2h, then immersing it in an ethyl silicate solution, ultrasonically treating it, standing it in the solution at room temperature for 48h, vacuum drying, using a picosecond laser to clean the surface of the silicone rubber rough sheet except the drilling area, and finally immersing it in a 20wt% hexamethyldisilazane solution, heating it to 35°C for reaction for 2h, and vacuum drying it to obtain a super-hydrophobic silicone rubber sheet; the laser drilling treatment is a periodic array structure surface treatment, and its parameters include: hole radius 100μm, hole spacing 154μm, and hole depth 400μm;

[0036] The remaining steps are the same as those in Example 1.

[0037] Embodiment 3: A preparation process of a silicone rubber sheet for mixing bone cement: comprising the following steps: S3: treating the surface of the cleaned silicone rubber original sheet with a nanosecond laser, then laser drilling the surface with a picosecond laser, and ultrasonic cleaning with ethanol to obtain a silicone rubber rough sheet; immersing the silicone rubber rough sheet in an 8wt% polydiallyldimethylammonium chloride solution, ultrasonically treating it, taking it out and drying it in a 50°C environment for 2h, then immersing it in an ethyl silicate solution, ultrasonically treating it, standing it in the solution at room temperature for 48h, vacuum drying, using a picosecond laser to clean the surface of the silicone rubber rough sheet except the drilling area, and finally immersing it in a 20wt% hexamethyldisilazane solution, heating it to 35°C for reaction for 2h, and vacuum drying it to obtain a super-hydrophobic silicone rubber sheet; the laser drilling treatment is a periodic array structure surface treatment, and its parameters include: hole radius 100m, hole spacing 100μm, and hole depth 400μm;

[0038] The remaining steps are the same as those in Example 1.

[0039] Comparative Example 1: A process for preparing a silicone rubber sheet for mixing bone cement: comprising the following steps: S1: preheating the kneading machine at 30°C for 5 minutes, adjusting the roller distance to 4mm, adding 100 parts of silicone rubber, mixing for 5 minutes, reducing the roller distance by 2mm, adding 5 parts of fluorosilicone rubber and 1.6 parts of disulfide in sequence, mixing for 10 minutes, increasing the roller distance by 3mm, making tablets, standing at room temperature, placing the tablets on a flat vulcanizer and vulcanizing at 175°C for 10 minutes to obtain silicone rubber original sheets;

[0040] The remaining steps are the same as those in Example 1.

[0041] Comparative Example 2: A process for preparing a silicone rubber sheet for mixing bone cement: comprising the following steps: S1: preheating the kneading machine at 30°C for 5 minutes, adjusting the roller distance to 4mm, adding 100 parts of silicone rubber, mixing for 5 minutes, reducing the roller distance by 2mm, adding 5 parts of polytetrafluoroethylene, mixing for 10 minutes, adding 1.6 parts of a disulfide, mixing for 10 minutes, expanding the roller distance by 3mm, making tablets, standing at room temperature, placing the tablets on a flat vulcanizer and vulcanizing at 175°C for 10 minutes to obtain silicone rubber original sheets;

[0042] The remaining steps are the same as those in Example 1.

[0043] Comparative Example 3: A preparation process for a silicone rubber sheet for mixing bone cement: comprising the following steps: S3: treating the surface of the cleaned silicone rubber original sheet with a nanosecond laser, then performing laser drilling treatment on the surface with a picosecond laser, and ultrasonic cleaning with ethanol to obtain a silicone rubber rough sheet; immersing the silicone rubber rough sheet in an 8wt% polydiallyldimethylammonium chloride solution, ultrasonically treating it, taking it out and drying it in a 50°C environment for 2h, then immersing it in an ethyl silicate solution, ultrasonically treating it, standing it in the solution at room temperature for 48h, vacuum drying, using a picosecond laser to clean the surface of the silicone rubber rough sheet except for the drilling area, and finally immersing it in a 20wt% hexamethyldisilazane solution, heating it to 35°C for reaction for 2h, and vacuum drying it to obtain a super-hydrophobic silicone rubber sheet; the laser drilling treatment is a periodic array structure surface treatment, and its parameters include: hole radius 200μm, hole spacing 200μm, and hole depth 400μm;

[0044] The remaining steps are the same as those in Example 1.

[0045] Comparative Example 4: A preparation process for a silicone rubber sheet for mixing bone cement: comprising the following steps: S3: treating the surface of the cleaned silicone rubber original sheet with a nanosecond laser, then performing laser drilling treatment on the surface with a picosecond laser, and ultrasonic cleaning with ethanol to obtain a silicone rubber rough sheet; immersing the silicone rubber rough sheet in an 8wt% polydiallyldimethylammonium chloride solution, ultrasonically treating it, taking it out and drying it in a 50°C environment for 2h, then immersing it in an ethyl silicate solution, ultrasonically treating it, standing it in the solution at room temperature for 48h, vacuum drying, using a picosecond laser to clean the surface of the silicone rubber rough sheet except for the drilling area, and finally immersing it in a 20wt% hexamethyldisilazane solution, heating it to 35°C for reaction for 2h, and vacuum drying it to obtain a super-hydrophobic silicone rubber sheet; the laser drilling treatment is a periodic array structure surface treatment, and its parameters include: hole radius 200μm, hole spacing 5150m, and hole depth 400μm;

[0046] The remaining steps are the same as those in Example 1.

[0047] Comparative Example 5: A process for preparing a silicone rubber sheet for mixing bone cement: comprising the following steps: S3: treating the surface of the cleaned silicone rubber original sheet with a nanosecond laser, and then ultrasonically cleaning it with ethanol to obtain a silicone rubber rough sheet; immersing the silicone rubber rough sheet in an 8wt% polydiallyldimethylammonium chloride solution, ultrasonically treating it, taking it out and drying it at 50°C for 2h, then immersing it in an ethyl silicate solution, ultrasonically treating it, standing it in the solution at room temperature for 48h, vacuum drying it, using a picosecond laser to clean the surface of the silicone rubber rough sheet except for the drilling area, and finally immersing it in a 20wt% hexamethyldisilazane solution, heating it to 35°C for reaction for 2h, and vacuum drying it to obtain a super-hydrophobic silicone rubber sheet;

[0048] The remaining steps are the same as those in Example 1.

[0049] Comparative Example 6: A process for preparing a silicone rubber sheet for mixing bone cement: comprising the following steps: S3: treating the surface of the cleaned silicone rubber original sheet with a nanosecond laser, then performing laser drilling treatment on the surface with a picosecond laser, and ultrasonic cleaning with ethanol to obtain a silicone rubber rough sheet; immersing the silicone rubber rough sheet in an 8wt% polydiallyldimethylammonium chloride solution, ultrasonically treating it, taking it out and drying it in a 50°C environment for 2h, then immersing it in an ethyl silicate solution, ultrasonically treating it, standing it in the solution at room temperature for 48h, vacuum drying it, and finally immersing it in a 20wt% hexamethyldisilazane solution, heating it to 35°C for reaction for 2h, and vacuum drying it to obtain a super-hydrophobic silicone rubber sheet; the laser drilling treatment is a periodic array structure surface treatment, and its parameters include: hole radius 100μm, hole spacing 258μm, and hole depth 400μm;

[0050] The remaining steps are the same as those in Example 1.

[0051] Experiment: High temperature friction performance test: A multifunctional material surface performance comprehensive tester was used to conduct a friction test at 100°C. The friction mode was reciprocating friction, and the friction pair was a GCr15 steel ball with a diameter of 6mm. The friction test load was 5N, the motor speed was 300r / min, and relative motion occurred between the sample and the ball. The friction coefficient measured for 60min was the dynamic friction coefficient. The contact angle of the silicone rubber plate before and after friction was measured.

[0052] Antibacterial performance test: Escherichia coli and Staphylococcus aureus suspension (25 μL, 2×10 4 CFUmL -1 ) was dropped on the surface of ordinary commercial silicone rubber plates and silicone rubber plates, and incubated at 37°C for 4 hours. Then 2 mL of LB medium was added to dilute the bacteria, and 10 μL of the bacterial suspension was applied to the LB agar plate. After incubation at 37°C for 18 hours, the visible bacterial colonies were counted, and the antibacterial properties after high-temperature friction were tested using the same method. Ordinary commercial silicone rubber plates were used as the negative control group.

[0053] Antibacterial activity (%) = N阴性对照组 -N 硅橡胶板 / N 阴性对照组 ×100%.

[0054] The experimental data are shown in Table 1 below.

[0055] Table 1 Silicone rubber sheet performance test data table

[0056]

[0057] Conclusion: The silicone rubber sheet prepared by the present invention has excellent high temperature friction resistance and antibacterial properties.

[0058] Comparative Example 1 lacks polytetrafluoroethylene, and Comparative Example 2 lacks fluorosilicone rubber, resulting in reduced high temperature friction resistance. The reason is that under high temperature conditions, the rubber matrix becomes soft and the fluidity increases. The lack of polytetrafluoroethylene dispersed in the rubber matrix plays a friction-reducing role, and the friction coefficient curve is stable. At the same time, the lack of the introduction of fluorosilicone rubber makes silicone rubber and polytetrafluoroethylene have good compatibility and stable friction state at high temperatures.

[0059] In Comparative Example 3, increasing the hole radius leads to a decrease in high temperature friction resistance. The reason is that the surface area fraction of silica in the hole is reduced, and it can no longer provide important support during the wear process, reduce the direct force on the silicone rubber area, and reduce the loss and deformation of silica in the hole.

[0060] In Comparative Example 4, increasing the pore spacing results in a decrease in high temperature friction resistance. The reason is that the contact between the droplet and the surface presents a coexistence of Wenze1 and Cassie. Since the liquid tends to move spontaneously from the high hydrophobic area to the low hydrophobic area, on the surface with a larger pore spacing, the water droplet is more likely to contact the silicone rubber area that has lost its hydrophobicity, and the micro-nano hydrophobic structure is weakened.

[0061] In Comparative Example 5, only the surface was treated with nanosecond laser, resulting in a decrease in high temperature friction resistance. The reason is that before friction, the laser-processed surface initially presents a hierarchical micro-nano structure with dense papillary nanoparticles attached, which mainly contributes to the surface super-hydrophobicity. Under the action of pressure and friction, the fragile nanoscale particles on the surface are quickly worn away, and the surface roughness of the sample decreases slightly; with the continuous friction between the surface and the sandpaper, the papillary nanoparticles almost disappear, and even some grooves plowed by sand particles can be observed, causing the surface roughness of the sample to increase rapidly. At the same time, the droplets on the surface of the sample will be immersed in these microscale grooves, and the contact state with the surface will change from the Cassie state to the Wenzel state, resulting in the loss of super-hydrophobicity.

[0062] In Comparative Example 6, the surface coating of the silicone rubber surface except for the holes was not cleaned, resulting in reduced high temperature friction resistance. Although the silica coating showed satisfactory superhydrophobicity, it was easy to crack and peel off on the soft silicone rubber substrate due to its excessive thickness and high hardness. Chemical changes in the silicone rubber area or silica residues caused its wear resistance to decrease.

[0063] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A process for preparing a silicone rubber sheet for mixing bone cement, characterized in that: The following steps are involved: S1: Add silicone rubber, fluorosilicone rubber and disulfide into a kneader, adjust the roller distance, make tablets, and vulcanize to obtain silicone rubber raw sheets; S2: Cut the silicone rubber sheet into pieces, clean it ultrasonically in ethanol, and set it aside; S3: The surface of the cleaned silicone rubber original sheet is treated with a nanosecond laser and then with a picosecond laser for laser drilling, and then the holes are filled with nano-silicon dioxide prepared by hydrolysis and condensation of ethyl silicate, and the surface except the drilling area is cleaned with a picosecond laser, and finally a super-hydrophobic silicone rubber sheet is obtained by hydrophobic modification with hexamethyldisilazane; S4: The surface of the super-hydrophobic silicone rubber sheet is modified with thiol groups, and ammonium bromide is grafted onto the surface through an ultraviolet light thiol-olefin reaction, and then grafted through an L-proline reaction, and finally nitric oxide is absorbed to saturation to obtain a silicone rubber sheet for bone cement mixing.

2. The process for preparing a silicone rubber sheet for mixing bone cement according to claim 1, characterized in that: The following steps are involved: S1: After preheating the kneading machine, adjust the roller distance, add silicone rubber, mix for 5-6 minutes, reduce the roller distance, add polytetrafluoroethylene, mix for 10-15 minutes, add fluorosilicone rubber and disulfide in sequence, mix for 10-15 minutes, expand the roller distance, make tablets, let stand at room temperature, and place the tablets on a flat vulcanizer for vulcanization to obtain silicone rubber original sheets; S2: Cut the silicone rubber sheet into pieces, clean it ultrasonically in ethanol, and set it aside; S3: After the surface of the cleaned silicone rubber original sheet is treated with a nanosecond laser, the surface is laser drilled with a picosecond laser, and ultrasonic cleaning is performed with ethanol to obtain a silicone rubber rough plate; the silicone rubber rough plate is immersed in an 8-10wt% polydiallyldimethylammonium chloride solution, ultrasonically treated, taken out and dried in a 50-55°C environment for 2-2.5h, and then immersed in an ethyl silicate solution, ultrasonically treated, and allowed to stand in the solution at room temperature for 48-60h, vacuum dried, and the surface of the silicone rubber rough plate except the drilling area is cleaned with a picosecond laser, and finally immersed in a 20-25wt% hexamethyldisilazane solution, heated to 35-45°C for reaction for 2-3h, and vacuum dried to obtain a superhydrophobic silicone rubber plate; S4: Immerse the super-hydrophobic silicone rubber sheet in a methanol solution containing 10-15wt% 3-mercaptopropyltrimethoxysilane and 1% W / V potassium hydroxide, heat to 50-55°C for reaction for 6-6.5h, immerse in methanol, ultrasonicate, and finally immerse in dichloromethane and stir for 3-3.5h to obtain a mercapto-modified silicone rubber sheet; under a nitrogen atmosphere, ammonium bromide, 2-methyl-2-acrylic acid-2-(2-methoxyethoxy)ethyl ester, 2,2-dimethoxy-2- Phenyl acetophenone is added to methanol, stirred evenly, and dripped onto the surface of the thiol-modified silicone rubber sheet, irradiated with ultraviolet light for 1-1.5 hours, washed with methanol and deionized water, and vacuum dried to obtain an ammonium bromide-modified silicone rubber sheet; the ammonium bromide-modified silicone rubber sheet is immersed in an 8-12wt% L-proline solution, stirred at room temperature for 12-14 hours, ventilated with nitrogen for 30-45 minutes, and then nitric oxide is introduced to saturation, and the solution is kept warm for absorption for 1-1.5 hours to obtain a silicone rubber sheet for bone cement blending.

3. The process for preparing a silicone rubber sheet for mixing bone cement according to claim 2, characterized in that: During the preparation of the silicone rubber sheet, the proportions of each component by mass include: 90-100 parts of silicone rubber, 5-10 parts of polytetrafluoroethylene, 5-10 parts of fluorosilicone rubber, and 1.6-2 parts of disulfide.

4. The process for preparing a silicone rubber sheet for mixing bone cement according to claim 2, characterized in that: The adjusting roller distance is 4-6mm, the reducing roller distance is 2-3mm, and the expanding roller distance is 3-4mm.

5. The process for preparing a silicone rubber sheet for mixing bone cement according to claim 2, characterized in that: The laser drilling process is a periodic array structure surface treatment, and its parameters include: hole radius 100 μm, hole spacing 100-258 μm, and hole depth 400 μm.

6. The process for preparing a silicone rubber sheet for mixing bone cement according to claim 2, characterized in that: The ethyl silicate solution consists of deionized water, anhydrous ethanol, ammonium hydroxide and ethyl silicate in a molar ratio of 0.5:1:1:3.

5.

7. The process for preparing a silicone rubber sheet for mixing bone cement according to claim 2, characterized in that: The preparation method of ammonium bromide comprises the following steps: adding 2-(dimethylamino)ethyl acrylate and 1-bromooctane into acetonitrile, stirring evenly, heating to 45-50° C. and reacting for 3 days to obtain ammonium bromide.

8. The process for preparing a silicone rubber sheet for mixing bone cement according to claim 7, characterized in that: In the preparation process of ammonium bromide, the molar ratio of 2-(dimethylamino)ethyl acrylate:1-bromooctane is 1:

1.

9. The process for preparing a silicone rubber sheet for mixing bone cement according to claim 2, characterized in that: In the preparation process of the ammonium bromide modified silicone rubber sheet, the molar ratio of ammonium bromide:2-methyl-2-acrylic acid-2-(2-methoxyethoxy)ethyl ester is 1:

1.

10. The silicone rubber sheet for bone cement mixing prepared according to the preparation process of the silicone rubber sheet for bone cement mixing according to any one of claims 1 to 9.

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