Super-hydrophilic antibacterial polyether-ether-ketone medical material and preparation method thereof

Abstract

The invention relates to the technical field of new medical materials, in particular to a super-hydrophilic antibacterial polyether-ether-ketone medical material and a preparation method thereof.The material is a polyether-ether-ketone material with the surface grafted with organosilicon quaternary ammonium salt, the surface of the material is provided with a nanometer protruding structure, the surface water contact angle is smaller than or equal to 5 degrees, the antibacterial rate to escherichia coli and staphylococcus aureus is larger than or equal to 97%, and the antibacterial rate to escherichia coli and staphylococcus aureus is larger than or equal to 97%. According to the super-hydrophilic antibacterial polyether-ether-ketone medical material and the preparation method thereof, the preparation process is simple and efficient, reaction conditions are mild, and the super-hydrophilic antibacterial polyether-ether-ketone medical material has wide universality and can be applied to large-scale production; meanwhile, the super-hydrophilic modified polyether-ether-ketone material with the antibacterial property on the surface can be applied to the field of medical instrument materials and has a very strong application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of medical new materials, and particularly to a superhydrophilic antibacterial polyetheretherketone medical material and a preparation method thereof. Background Art

[0002] Polyetheretherketone (PEEK) is a semi-crystalline polymer whose main chain is composed of benzene rings, ketone carbonyl groups and ether groups, and has excellent mechanical properties, corrosion resistance, wear resistance, natural ray permeability and biocompatibility and other excellent properties. Therefore, its special molecular structure determines its excellent physical properties and stable chemical properties. After crystallization, the molecular chains of polyetheretherketone are closely and regularly stacked, and it has outstanding acid, alkali and solvent resistance. Since the development of polyetheretherketone resin, due to its excellent load-bearing capacity, wear resistance, flame retardancy and chemical inertness, it has the trend of replacing traditional metal materials for manufacturing various parts of airplanes, weapon machinery and automobiles; due to its excellent solvent and high-temperature resistance, it is used in pump bodies, piston rings and valves and other components in the petroleum industry and nuclear industry; due to its outstanding hydrolysis resistance and biocompatibility and other characteristics, it is widely used in the field of biological implants, such as it can be used as a substitute for artificial bones, spines, joints and mandibles, etc.; it is also widely used in the field of medical devices such as disinfection boxes and medical catheters. However, the water contact angle of polyetheretherketone is about 82.43±2.50°, and the adhesion force of the bacterial liquid on the material surface is too large. Since PEEK itself does not have antibacterial adhesion and sterilization properties, various liquids or microorganisms are extremely likely to adhere to the surface of the PEEK material, causing pollution, seriously affecting various properties and service life of polyetheretherketone, and there may be a hidden danger of spreading pathogens when used in the field of medical devices. Therefore, surface modification to endow the PEEK material with antibacterial and antifouling properties is a problem that must be solved in the process of using the polyetheretherketone material in the field of medical device materials.

[0003] The material with super-hydrophilic surface has excellent anti-bacterial adhesion and antibacterial properties, which can effectively solve the problems of various bacteria adhering to the surface of the material and causing pollution during the use of polyetheretherketone resin. When preparing polyetheretherketone materials with super-hydrophilic properties, the traditional idea is to initiate a hydrophilic modified monomer grafting reaction in the polyetheretherketone hollow fiber. Patent CN108854606A discloses a super-hydrophilic polyetheretherketone material and a preparation method thereof, wherein the polyetheretherketone hollow fiber membrane is placed in a container, a hydrophilic modified monomer solution and ammonium ferrous sulfate are added thereto, and the polyetheretherketone hollow fiber membrane is immersed therein, and the obtained polyetheretherketone hollow fiber membrane is placed in an ultraviolet radiation box for irradiation, so that it undergoes a surface photografting reaction, and a polyetheretherketone having a layer of super-hydrophilic polymer on the surface is obtained. However, in this method, ultraviolet-induced polymerization requires the use of ultraviolet light sources of specific wavelengths, which may have limited penetration of some materials, especially on thicker layers or opaque substrates, where the penetration of ultraviolet rays is poor, resulting in incomplete polymerization and high cost. And because ultraviolet rays may cause damage to human eyes and skin, which is harmful to the human body, therefore, in view of the above situation, there is an urgent need to develop a super hydrophilic antibacterial polyetheretherketone medical material and a preparation method thereof to overcome the shortcomings in current practical applications. Summary of the invention

[0004] The object of the present invention is to provide a super-hydrophilic antibacterial polyetheretherketone medical material and a preparation method thereof, so as to solve the problems raised in the above-mentioned background technology.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A super-hydrophilic antibacterial polyetheretherketone medical material is a polyetheretherketone material with a surface grafted with a silicone quaternary ammonium salt, the surface of which has a nano-protrusion structure, a surface water contact angle of ≤5°, and an antibacterial rate of ≥97% against Escherichia coli and Staphylococcus aureus.

[0007] As a further embodiment of the present invention: the organosilicon quaternary ammonium salt is any one of 3-(trimethoxysilyl)propyldimethyldodecylammonium chloride, 3-(trimethoxysilyl)propyldimethyltetradecylammonium chloride, 3-(trimethoxysilyl)propyldimethylhexadecylammonium chloride or 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride.

[0008] As a further solution of the present invention: the height of the nanoprotrusion structure is 20-200nm.

[0009] A method for preparing the super-hydrophilic antibacterial polyetheretherketone medical material according to the above-mentioned method comprises the following steps:

[0010] S1. Cleaning treatment: ultrasonically clean the PEEK material with acetone, ethanol and ultrapure water in sequence;

[0011] S2. Plasma activation: Treat the cleaned polyetheretherketone material with glow discharge plasma to obtain an activated polyetheretherketone material with a nano-protrusion structure on the surface;

[0012] S3. Hydroxylation treatment: React the material obtained in step S2 in a hydroxylation solution, and after cleaning and drying, obtain a hydroxylated polyetheretherketone material;

[0013] S4. Surface grafting: React the material obtained in step S3 in an organosilicon quaternary ammonium salt solution, and after cleaning and drying, obtain the superhydrophilic and antibacterial polyetheretherketone medical material.

[0014] As a further solution of the present invention: In step S2, the atmosphere of the glow discharge plasma treatment is O2, Ar or a mixed gas of O2 and Ar, the gas flow rate is 40 - 200 ml / min, and the treatment time is 2 - 30 min.

[0015] As a further solution of the present invention: In step S3, the hydroxylation solution is a dimethyl sulfoxide solution of sodium borohydride, the concentration is 0.2 - 1 g / 50 ml, the reaction temperature is 70 - 150 °C, and the reaction time is 1 - 8 h.

[0016] As a further solution of the present invention: In step S4, the concentration of the organosilicon quaternary ammonium salt solution is 5 - 20 wt%, the reaction temperature is 20 - 50 °C, the reaction time is 1 - 6 h, the reaction pH is 1 - 6, and the drying temperature is 50 - 60 °C.

[0017] As a further solution of the present invention: In step S1, the cleaning treatment includes ultrasonically cleaning the polyetheretherketone material with acetone, ethanol and ultrapure water in sequence for 1 - 3 times each, and each time for 5 - 15 minutes.

[0018] As a further solution of the present invention: In step S4, the organosilicon quaternary ammonium salt solution is an ethanol solution.

[0019] A medical device is made of the above-mentioned superhydrophilic and antibacterial polyetheretherketone medical material, and the medical device includes an artificial joint, a disinfection box or a medical catheter.

[0020] Compared with the prior art, the beneficial effects of the present invention are:

[0021] 1. The present invention provides a method of physical and chemical synergistic modification, that is, introducing a nano-hilly structure on the surface of the polyetheretherketone resin matrix to increase the surface area and activate the surface, and then treating the surface with sodium borohydride to obtain a hydroxylated polyetheretherketone material with a nano-hilly structure on the surface;

[0022] 2. The physical method of plasma treatment and the chemical method of sodium borohydride treatment involved in the present invention are only carried out on the surface of the polyetheretherketone material, without affecting its own structure and properties;

[0023] 3. 3-(Trimethoxysilyl)propyl dimethyldodecylammonium chloride used in the present invention is an organosilicon quaternary ammonium salt, and a trace concentration can produce a powerful bactericidal ability against bacteria;

[0024] 4. The treatment methods and reagents involved in the present invention are all low-cost, green, environmentally friendly, convenient and efficient, and harmless to the human body;

[0025] 5. The preparation process of the present invention is simple and efficient, the reaction conditions are mild, and it has wide universality and can be applied to large-scale production; at the same time, the superhydrophilic modified polyetheretherketone material with antibacterial properties on the surface can be used in the field of medical device materials and has extremely strong application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic flow chart of the preparation method of the superhydrophilic polyetheretherketone material with antibacterial and anti-adhesion properties on the surface in the embodiment of the present invention.

[0027] Figure 2 It is an XPS diagram of the modified polyetheretherketone material with antibacterial properties on the surface prepared in Example 5 of the present invention;

[0028] Among them, PEEK is untreated polyetheretherketone, and PEEK-P-Q is polyetheretherketone after superhydrophilic modification on the surface.

[0029] Figure 3 It is a static water contact angle diagram of the surface of the polyetheretherketone material before and after modification treatment in Example 5 of the present invention at room temperature and atmospheric pressure;

[0030] Among them, PEEK is untreated polyetheretherketone, PEEK-OH is hydroxylated polyetheretherketone, and PEEK-P-Q is polyetheretherketone after superhydrophilic modification on the surface.

[0031] Figure 4 It is an SEM diagram of the surface of the untreated polyetheretherketone material in Example 5 of the present invention.

[0032] Figure 5 It is an SEM diagram of the surface of the polyetheretherketone after plasma activation and hydroxylation in Example 5 of the present invention.

[0033] Figure 6 It is an SEM diagram of the surface of the polyetheretherketone after superhydrophilic modification on the surface in Example 5 of the present invention.

[0034] Figure 7 It is a schematic diagram of the experimental results of Escherichia coli plating in the embodiment of the present invention;

[0035] Among them, the left figure is a bacterial plating diagram of Escherichia coli on untreated polyetheretherketone, and the right figure is a bacterial plating diagram of Escherichia coli on polyetheretherketone after surface superhydrophilic modification.

[0036] Figure 8 This is a schematic diagram of the experimental results of Staphylococcus aureus plating in the embodiments of the present invention;

[0037] Among them, the left figure is a bacterial plating diagram of Staphylococcus aureus on untreated polyetheretherketone, and the right figure is a bacterial plating diagram of Staphylococcus aureus on polyetheretherketone after surface superhydrophilic modification.

[0038] Figure 9 This is a schematic diagram of the experimental results of viable and dead Escherichia coli bacteria in the embodiments of the present invention;

[0039] Among them, the left figure is the staining result of viable and dead Escherichia coli bacteria on untreated polyetheretherketone, and the right figure is the staining result of viable and dead Escherichia coli bacteria on polyetheretherketone after superhydrophilic modification treatment.

[0040] Figure 10 This is a schematic diagram of the experimental results of viable and dead Staphylococcus aureus bacteria in the embodiments of the present invention;

[0041] Among them, the left figure is the staining result of viable and dead Staphylococcus aureus bacteria on untreated polyetheretherketone, and the right figure is the staining result of viable and dead Staphylococcus aureus bacteria on polyetheretherketone after superhydrophilic modification treatment. Detailed implementation manners

[0042] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0043] The following describes the specific implementation of the present invention in detail with specific embodiments.

[0044] Please refer to Figures 1 - 10 , a superhydrophilic antibacterial polyetheretherketone medical material provided by an embodiment of the present invention. The material is a polyetheretherketone material grafted with organosilicon quaternary ammonium salt on the surface, has a nano-protrusion structure on the surface, and the surface water contact angle ≤ 5°, and the antibacterial rate against Escherichia coli and Staphylococcus aureus ≥ 97%.

[0045] The organosilicon quaternary ammonium salt is any one of 3-(trimethoxysilyl)propyl dimethyldodecylammonium chloride, 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride, 3-(trimethoxysilyl)propyl dimethylhexadecylammonium chloride, or 3-(trimethoxysilyl)propyl dimethyloctadecylammonium chloride.

[0046] The height of the nano-protrusion structure is 20 - 200 nm.

[0047] In one embodiment of the present invention, refer to Figures 1 - 10 , a preparation method of the superhydrophilic antibacterial polyetheretherketone medical material according to the above, comprising the following steps:

[0048] S1. Cleaning treatment: Ultrasonically clean the PEEK material successively with acetone, ethanol, and ultrapure water.

[0049] S2. Plasma activation: Treat the cleaned polyetheretherketone material with glow discharge plasma to obtain an activated polyetheretherketone material with a nano-protrusion structure on the surface.

[0050] S3. Hydroxylation treatment: Place the material obtained in step S2 in a hydroxylation solution for reaction, and after cleaning and drying, obtain a hydroxylated polyetheretherketone material.

[0051] S4. Surface grafting: Place the material obtained in step S3 in an organosilicon quaternary ammonium salt solution for reaction, and after cleaning and drying, obtain the superhydrophilic antibacterial polyetheretherketone medical material.

[0052] In one embodiment of the present invention, in step S2, the atmosphere of the glow discharge plasma treatment is O2, Ar, or a mixed gas of O2 and Ar, the gas flow rate is 40 - 200 ml / min, and the treatment time is 2 - 30 min.

[0053] In step S3, the hydroxylation solution is a dimethyl sulfoxide solution of sodium borohydride, with a concentration of 0.2 - 1 g / 50 ml, a reaction temperature of 70 - 150 °C, and a reaction time of 1 - 8 h.

[0054] In step S4, the concentration of the organosilicon quaternary ammonium salt solution is 5 - 20 wt%, the reaction temperature is 20 - 50 °C, the reaction time is 1 - 6 h, the reaction pH is 1 - 6, and the drying temperature is 50 - 60 °C.

[0055] In step S1, the cleaning treatment includes ultrasonically cleaning the polyetheretherketone material with acetone, ethanol, and ultrapure water successively for 1 - 3 times, 5 - 15 minutes each time.

[0056] In step S4, the organosilicon quaternary ammonium salt solution is an ethanol solution.

[0057] In one embodiment of the present invention, a medical device is made of the above-mentioned superhydrophilic antibacterial polyetheretherketone medical material, and the medical device includes an artificial joint, a disinfection box or a medical catheter.

[0058] In summary, for the preparation method of the superhydrophilic antibacterial polyetheretherketone medical material of the present invention, with reference to Figure 1 , the method includes:

[0059] S1. Preparation of clean polyetheretherketone resin:

[0060] The polyetheretherketone resin is polished with 200#, 400#, 600#, 800#, 1000#, 2000# SiC sandpaper to remove surface stains, and then ultrasonically cleaned with acetone, ethanol and deionized water respectively, and dried to obtain clean polyetheretherketone resin;

[0061] S2. Preparation of polyetheretherketone material with nano-protrusion structure and active sites on the surface:

[0062] The clean polyetheretherketone material obtained in step S1 is placed in a glow discharge plasma reaction chamber, the treatment time is set to 1 - 30 min, the vacuum of the reaction chamber is evacuated, and after the reaction chamber is in a vacuum state, the gas valve switch is opened. The atmosphere for plasma treatment is one of O2, Ar, and a mixed gas of O2 and Ar. The gas flow rate is adjusted to 40 - 200 ml / min. After the treatment is completed, the vacuum of the reaction chamber is removed, the gas valve switch is closed, and the sample is taken out;

[0063] S3. Preparation of polyetheretherketone material with nano-protrusion structure and hydroxylated surface:

[0064] 0.2 - 1 g of NaBH4 as a hydroxylation agent is configured into a 50 ml dimethyl sulfoxide solution. The polyetheretherketone material with a nano-protrusion structure on the surface obtained in the previous step is placed in the solution, the reaction temperature is set to 70 - 150 °C, and the reaction is carried out for 1 - 8 h. Then it is ultrasonically cleaned with methanol, 0.5 mol hydrochloric acid and deionized water, and dried to obtain a hydroxylated polyetheretherketone material with a nano-protrusion structure on the surface, which is stored in a clean environment for later use;

[0065] S4. Preparation of polyetheretherketone material with nano-protrusion structure and superhydrophilic surface:

[0066] The polyetheretherketone material with a nano-protrusion structure and hydroxylated surface prepared in S3 is placed in a 5 - 20 wt% ethanol solution of 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride, the reaction temperature is set to 25 - 50 °C, the reaction time is 1 - 8 h, and it is dried at 50 - 60 °C for later use.

[0067] The present invention will be further described below with reference to embodiments.

[0068] Example 1:

[0069] The polyetheretherketone resin (with a thickness of 300 μm and a length × width of 1.2 cm × 1.2 cm) was polished with 200#, 400#, 600#, 800#, 1000#, and 2000# SiC sandpapers to remove surface stains, and then ultrasonically cleaned with acetone, ethanol, and deionized water respectively, and dried to obtain a clean polyetheretherketone material; the polyetheretherketone material with a nano-protrusion structure on the surface was placed in a glow discharge plasma reaction chamber, the treatment time was set to 2 min, the vacuum of the reaction chamber was evacuated, after the reaction chamber was in a vacuum state, the gas valve switch was opened, the atmosphere for plasma treatment was a mixed gas of O2 and Ar, the gas flow rate was adjusted to 40 ml / min, after the treatment was completed, the vacuum of the reaction chamber was removed, the gas valve switch was closed, and the sample was taken out; 0.2 g of NaBH4 was configured into a 50 ml dimethyl sulfoxide solution, the reaction temperature was set to 70 °C, and the reaction was carried out for 1 h; the surface modifier 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride was configured into an ethanol solution with a concentration of 5 wt%, and the obtained polyetheretherketone material with nano-protrusion hydroxylation on the surface was placed in an ethanol solution of 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride with a concentration of 5 wt%, the reaction temperature was set to 20 °C, the pH was 6, the reaction was carried out for 2 h, and then dried at 60 °C to obtain a superhydrophilic polyetheretherketone material with a nano-protrusion structure on the surface, which was stored in a clean environment for standby.

[0070] Example 2:

[0071] The polyetheretherketone resin (with a thickness of 300 μm and a length × width of 1.2 cm × 1.2 cm) was polished with 200#, 400#, 600#, 800#, 1000#, and 2000# SiC sandpapers to remove surface stains, and then ultrasonically cleaned with acetone, ethanol, and deionized water respectively, and dried to obtain a clean polyetheretherketone material; the polyetheretherketone material with a nano-protrusion structure on the surface was placed in a glow discharge plasma reaction chamber, the treatment time was set to 4 min, the vacuum of the reaction chamber was pumped, and after the reaction chamber was in a vacuum state, the gas valve switch was opened. The atmosphere for plasma treatment was a mixed gas of O2 and Ar, the gas flow rate was adjusted to 60 ml / min, after the treatment was completed, the vacuum of the reaction chamber was removed, the gas valve switch was closed, and the sample was taken out; 0.4 g of NaBH4 was configured into a 50 ml dimethyl sulfoxide solution, the reaction temperature was set to 80 °C, and the reaction was carried out for 2 h; the surface modifier 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride was configured into an ethanol solution with a concentration of 5 wt%, and the obtained polyetheretherketone material with nano-protrusion hydroxylation on the surface was placed in an ethanol solution of 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride with a concentration of 5 wt%, the reaction temperature was set to 30 °C, the pH was 5, and the reaction was carried out for 3 h, and then dried at 60 °C to obtain a superhydrophilic polyetheretherketone material with a nano-protrusion structure on the surface, which was stored in a clean environment for standby.

[0072] Example 3:

[0073] The polyetheretherketone resin (with a thickness of 300 μm and a length × width of 1.2 cm × 1.2 cm) was polished with 200#, 400#, 600#, 800#, 1000#, and 2000# SiC sandpapers to remove surface stains, and then ultrasonically cleaned with acetone, ethanol, and deionized water respectively, and dried to obtain a clean polyetheretherketone material; the polyetheretherketone material with a nanoscale protrusion structure on the surface was placed in a glow discharge plasma reaction chamber, the treatment time was set to 6 min, the vacuum of the reaction chamber was pumped, and after the reaction chamber was in a vacuum state, the gas valve switch was opened. The atmosphere for plasma treatment was a mixed gas of O2 and Ar, the gas flow rate was adjusted to 80 ml / min, after the treatment was completed, the vacuum of the reaction chamber was removed, the gas valve switch was closed, and the sample was taken out; 0.6 g of NaBH4 was configured into a 50 ml dimethyl sulfoxide solution, the reaction temperature was set to 90 °C, and the reaction was carried out for 3 h; the surface modifier 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride was configured into an ethanol solution with a concentration of 5 wt%, and the obtained polyetheretherketone material with a nanoscale protrusion hydroxylated surface was placed in an ethanol solution of 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride with a concentration of 5 wt%, the reaction temperature was set to 30 °C, the pH was 4, and the reaction was carried out for 4 h, and then dried at 60 °C to obtain a superhydrophilic polyetheretherketone material with a nanoscale protrusion structure, which was stored in a clean environment for standby.

[0074] Example 4:

[0075] The polyetheretherketone resin (with a thickness of 300 μm and a length×width of 1.2 cm×1.2 cm) was polished with 200#, 400#, 600#, 800#, 1000#, and 2000# SiC sandpapers to remove surface stains, and then ultrasonically cleaned with acetone, ethanol, and deionized water respectively, and dried to obtain a clean polyetheretherketone material; the polyetheretherketone material with a nano-protrusion structure on the surface was placed in a glow discharge plasma reaction chamber, the treatment time was set to 8 min, the vacuum of the reaction chamber was evacuated, after the reaction chamber was in a vacuum state, the gas valve switch was opened, the atmosphere for plasma treatment was a mixed gas of O2 and Ar, the gas flow rate was adjusted to 100 ml / min, after the treatment was completed, the vacuum of the reaction chamber was removed, the gas valve switch was closed, and the sample was taken out; 0.8 g of NaBH4 was configured into a 50 ml dimethyl sulfoxide solution, the reaction temperature was set to 100 °C, and the reaction was carried out for 4 h; the surface modifier 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride was configured into an ethanol solution with a concentration of 5 wt%, the obtained polyetheretherketone material with nano-protrusion hydroxylation on the surface was placed in an ethanol solution of 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride with a concentration of 5 wt%, the reaction temperature was set to 40 °C, the pH was 3, and the reaction was carried out for 4 h, and then dried at 60 °C to obtain a superhydrophilic polyetheretherketone material with a nano-protrusion structure on the surface, which was stored in a clean environment for standby.

[0076] Example 5:

[0077] The polyetheretherketone resin (with a thickness of 300 μm and a length×width of 1.2 cm×1.2 cm) was polished with 200#, 400#, 600#, 800#, 1000#, and 2000# SiC sandpapers to remove surface stains, and then ultrasonically cleaned with acetone, ethanol, and deionized water respectively, and dried to obtain a clean polyetheretherketone material; the obtained polyetheretherketone material with a nano-protrusion structure on the surface was placed in a glow discharge plasma reaction chamber, the treatment time was set to 10 min, the vacuum of the reaction chamber was evacuated, after the reaction chamber was in a vacuum state, the gas valve switch was opened, the atmosphere for plasma treatment was a mixed gas of O2 and Ar, the gas flow rate was adjusted to 120 ml / min, after the treatment was completed, the vacuum of the reaction chamber was removed, the gas valve switch was closed, and the sample was taken out; 1 g of NaBH4 was configured into a 50 ml dimethyl sulfoxide solution, the reaction temperature was set to 110 °C, and the reaction was carried out for 54 h; the surface modifier 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride was configured into an ethanol solution with a concentration of 5 wt%, and the obtained polyetheretherketone material with nano-protrusion hydroxylation on the surface was placed in an ethanol solution of 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride with a concentration of 5 wt%, the reaction temperature was set to 50 °C, the pH was 2, the reaction was carried out for 5 h, and then dried at 60 °C to obtain a superhydrophilic polyetheretherketone material with a nano-protrusion structure on the surface, which was stored in a clean environment for standby.

[0078] Example 6:

[0079] In this example, the antibacterial performance of the material against the typical Gram-negative bacterium - Escherichia coli was evaluated by the bacterial plate counting experiment;

[0080] The untreated PEEK and the surface-modified PEEK-PQ were placed on the clean bench, and each side was irradiated with ultraviolet light for 1 h, and then the antibacterial property of the material was tested by the film sticking method. The samples irradiated with ultraviolet light were placed in a nine-well plate respectively, and 8 μl of Escherichia coli with a concentration of 1×10 7 CFU / ml was dropped on the surface of the 1.2 cm×1.2 cm material, and the bacterial solution was covered with a 1 cm×1 cm PET (polyethylene terephthalate) film, and cultured in an aerobic environment at 37 °C for 24 h. The samples were taken out and put into a centrifuge tube containing 1.6 ml of PBS buffer solution, ultrasonically oscillated for 3 min, 100 μl of the diluted oscillating solution was evenly spread on the LB agar plate, and cultured in an aerobic environment at 37 °C for 24 h. The agar plate was taken out, immediately photographed and the colonies were counted.

[0081] The antibacterial rate of the bacteria was calculated by the following formula:

[0082] Antibacterial rate = (CFU of the control group - CFU of the experimental group) / CFU of the control group × 100%.

[0083] The experimental results are asFigure 6 As shown, unmodified PEEK does not have antibacterial ability, and the antibacterial rate of PEEK-PQ is 97.8%, indicating that the PEEK-PQ material after surface super-hydrophilic grafting of organosilicon quaternary ammonium salt has excellent antibacterial ability against the typical Gram-negative bacterium - Escherichia coli.

[0084] Example 7:

[0085] In this example, the bacterial plate count experiment was used to evaluate the antibacterial performance of the material against the typical Gram-positive bacterium - Staphylococcus aureus;

[0086] The untreated PEEK and the surface-modified PEEK-PQ were placed on the clean bench and irradiated with ultraviolet light for 1 h on both the front and back sides. Then, the antibacterial property of the material was tested by the film sticking method. The samples irradiated with ultraviolet light were placed in 96-well plates respectively. 8 μl of Escherichia coli with a concentration of 1×10 7 CFU / ml was dropped on the surface of the 1.2 cm × 1.2 cm material, and a 1 cm × 1 cm PET (polyethylene terephthalate) film was used to cover the bacterial solution. It was cultured in an aerobic environment at 37 °C for 24 h. The samples were taken out and put into a centrifuge tube containing 1.6 ml of PBS buffer solution, and ultrasonically oscillated for 3 min. 100 μl of the diluted oscillating solution was evenly spread on the LB agar plate and cultured in an aerobic environment at 37 °C for 24 h. The agar plate was taken out, immediately photographed, and the colonies were counted.

[0087] The antibacterial rate of bacteria was calculated by the following formula:

[0088] Antibacterial rate = (CFU of the control group - CFU of the experimental group) / CFU of the control group × 100%.

[0089] The experimental results are as Figure 6 shown, unmodified PEEK does not have antibacterial ability, and the antibacterial rate of PEEK-PQ is 99.6%, indicating that the PEEK-PQ material after surface super-hydrophilic grafting of organosilicon quaternary ammonium salt has excellent antibacterial ability against the typical Gram-positive bacterium - Staphylococcus aureus.

[0090] Example 8:

[0091] In this example, the live / dead fluorescence staining experiment was used to evaluate important information on the bacterial attachment and growth behavior of the material against the typical Gram-negative bacterium - Escherichia coli and the typical Gram-positive bacterium - Staphylococcus aureus.

[0092] Mix 1 volume of Component A NucGreen and 2 volumes of Component B EthD-III in a microcentrifuge tube. After thorough mixing, add 8 volumes of 0.85% NaCl solution to obtain a 100× dye solution. Add 1 μL of the 100× dye solution to the surfaces of untreated PEEK and surface-modified PEEK-PQ material specimens. Mix well and incubate in the dark at room temperature for 15 min. After incubation, perform rinsing to wash away the residual dye. Observe live (green fluorescence) and dead (red fluorescence) bacteria in the FITC and Cy3 (or Texas Red) channels.

[0093] Therefore, the present invention uses a method of synergistic physical and chemical effects to perform surface modification on polyetheretherketone, preparing a superhydrophilic polyetheretherketone material with antifouling properties on the surface, achieving anti-adhesion and antibacterial adhesion properties on the material surface. At the same time, this method has the advantages of simple process, energy saving, environmental protection, and high efficiency.

[0094] It should be noted that in the present invention, it should be understood that although this specification is described according to the embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A superhydrophilic antibacterial polyetheretherketone medical material, characterized in that, The material is a polyetheretherketone material with surface-grafted organosilicon quaternary ammonium salt, which has a nano-protrusion structure on its surface, and the surface water contact angle ≤ 5°, and the antibacterial rate against Escherichia coli and Staphylococcus aureus ≥ 97%.

2. The superhydrophilic antibacterial polyetheretherketone medical material according to claim 1 and its preparation method, characterized in that, The organosilicon quaternary ammonium salt is any one of 3-(trimethoxysilyl)propyl dimethyldodecylammonium chloride, 3-(trimethoxysilyl)propyl dimethyltetradecylammonium chloride, 3-(trimethoxysilyl)propyl dimethylhexadecylammonium chloride, or 3-(trimethoxysilyl)propyl dimethyloctadecylammonium chloride.

3. The superhydrophilic antibacterial polyetheretherketone medical material according to claim 1 and its preparation method, characterized in that, The height of the nano-protrusion structure is 20 - 200 nm.

4. A method for preparing the superhydrophilic antibacterial polyetheretherketone medical material according to any one of claims 1-3, characterized in that, It includes the following steps: S1. Cleaning treatment: Ultrasonically clean the PEEK material successively with acetone, ethanol, and ultrapure water. S2. Plasma activation: Treat the cleaned polyetheretherketone material with glow discharge plasma to obtain an activated polyetheretherketone material with a nano-protrusion structure on its surface. S3. Hydroxylation treatment: Place the material obtained in step S2 in a hydroxylation solution for reaction, and after cleaning and drying, obtain a hydroxylated polyetheretherketone material. S4. Surface grafting: Place the material obtained in step S3 in an organosilicon quaternary ammonium salt solution for reaction, and after cleaning and drying, obtain the superhydrophilic antibacterial polyetheretherketone medical material.

5. The preparation method of the superhydrophilic antibacterial polyetheretherketone medical material according to claim 4, wherein, In step S2, the atmosphere of the glow discharge plasma treatment is O2, Ar, or a mixed gas of O2 and Ar, the gas flow rate is 40 - 200 ml / min, and the treatment time is 2 - 30 min.

6. The preparation method of the superhydrophilic antibacterial polyetheretherketone medical material according to claim 4, wherein In step S3, the hydroxylation solution is a dimethyl sulfoxide solution of sodium borohydride, with a concentration of 0.2 - 1 g / 50 ml, the reaction temperature is 70 - 150 °C, and the reaction time is 1 - 8 h.

7. The preparation method of the superhydrophilic antibacterial polyetheretherketone medical material according to claim 4, wherein In step S4, the concentration of the organosilicon quaternary ammonium salt solution is 5 - 20 wt%, the reaction temperature is 20 - 50 °C, the reaction time is 1 - 6 h, the reaction pH is 1 - 6, and the drying temperature is 50 - 60 °C.

8. The preparation method of the superhydrophilic antibacterial polyetheretherketone medical material according to claim 4, characterized in that, In step S1, the cleaning treatment includes ultrasonically cleaning the polyetheretherketone material with acetone, ethanol, and ultrapure water successively for 1 - 3 times, 5 - 15 minutes each time.

9. The preparation method of the superhydrophilic antibacterial polyetheretherketone medical material according to claim 4, characterized in that, In step S4, the organosilicon quaternary ammonium salt solution is an ethanol solution.

10. A medical device, characterized in that, It is made of the superhydrophilic antibacterial polyetheretherketone medical material according to any one of claims 1 - 3, and the medical device includes an artificial joint, a disinfection box, or a medical catheter.

Images