Conjugated polythiophene-polyether-ether-ketone-based highly antibacterial coating and preparation method thereof

Abstract

The invention relates to the technical field of polyether-ether-ketone composite materials, in particular to a conjugated polythiophene-polyether-ether-ketone-based high-antibacterial coating and a preparation method thereof.The preparation method comprises the steps that hydroxyl modified boron nitride with photocatalytic capacity and aminated PEEK are subjected to melt blending to generate chemical bonding, and a BN-OH / PEEK-NH2 composite fine powder material is formed; then carrying out oxidative polymerization on the BN-OH / PEEK-NH2 composite fine powder and a thiophene monomer under the action of an oxidizing agent, carrying out in-situ synthesis to obtain a polythiophene / BN-OH / PEEK-NH2 conjugated composite material, and subsequently spraying the polythiophene / BN-OH / PEEK-NH2 conjugated composite material to the surface of a base material to prepare a composite coating with excellent antibacterial property, high thermal stability and low friction coefficient; the antibacterial rate of the coating on escherichia coli and staphylococcus aureus under illumination reaches 90% or above, and the coating is suitable for the medical antibacterial field.

Description

Technical Field

[0001] The invention relates to the technical field of polyetheretherketone composite materials, and in particular to a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating and a preparation method thereof. Background Art

[0002] PEEK is a high-performance thermoplastic with excellent mechanical properties, chemical stability and thermal stability, and can withstand high temperatures up to 260°C. PEEK coating technology uses these characteristics of PEEK to attach PEEK materials to the surface of the substrate by spraying and other methods to improve the wear resistance and chemical corrosion resistance of the substrate. It is widely used in industry, oil and gas, automobiles, food processing, semiconductors, electronics, pharmaceuticals and other industries.

[0003] However, due to the high price of PEEK material itself, high biological inertness of coating, and lack of independent antibacterial properties, it is rarely used in the field of medical antibacterial. In the prior art, the antibacterial properties are improved by introducing photocatalytic materials (such as TiO2), but there are problems such as narrow light absorption range and insufficient high temperature stability. In order to solve the problems existing in the prior art, expand the application of PEEK coating in the field of medical antibacterial, and improve the antibacterial stability of coating, the present invention is proposed. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating and a preparation method thereof. The present invention is based on the composite of amino polyetheretherketone (PEEK-NH2), hydroxyl-modified boron nitride (BN-OH) and in-situ synthesized conjugated polythiophene to prepare a photocatalytic antibacterial coating. The coating obtained by the method of the present invention can enhance the light capture ability and realize the synergistic optimization of the high-efficiency antibacterial and high-temperature performance of the PEEK-based coating.

[0005] In order to achieve the above objectives, the present invention is implemented by the following technical solutions:

[0006] A method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating comprises the following steps:

[0007] S1, amino polyetheretherketone (PEEK-NH2) and hydroxyl-modified boron nitride (BN-OH) are uniformly mixed according to a proportion, and then melt-blended, extruded, granulated, and particle size refined in sequence to obtain composite fine powder (referred to as BN-OH / PEEK-NH2 composite fine powder);

[0008] S2, oxidatively polymerizing the composite fine powder and thiophene monomer under the action of an oxidant to in situ synthesize a conjugated polythiophene-polyetheretherketone composite material (referred to as a polythiophene / BN-OH / PEEK-NH2 conjugated composite material);

[0009] S3, electrostatically spraying the conjugated polythiophene composite material onto the pretreated surface of the metal substrate, and subjecting it to heat treatment, quenching and curing to form a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating.

[0010] Furthermore, the method for obtaining the amino polyetheretherketone described in S1 is:

[0011] S11, immersing the polyetheretherketone in a sodium borohydride solution, then drying, and then washing with an alcohol solution, water, an inorganic acid solution, water, and an alcohol solution in sequence to obtain hydroxylated polyetheretherketone (PEEK-OH); introducing amino groups into the molecular structure of PEEK by chemical modification to improve biocompatibility and reactivity;

[0012] S12, the hydroxylated polyetheretherketone is immersed in a hexamethylene diisocyanate solution with diazabicyclooctane as a catalyst in an inert atmosphere to react to obtain isocyanate polyetheretherketone (PEEK-NCO); high-temperature steam is used to treat BN powder to form a hydroxylated surface to enhance the reaction activity;

[0013] S13, placing the isocyanate-treated polyetheretherketone in a dioxane alkaline solution for reaction, washing and drying to obtain amino-treated polyetheretherketone (PEEK-NH2), wherein the mass percentage of amino groups in the obtained amino-treated polyetheretherketone is about 0.1wt%-1wt%.

[0014] Furthermore, in S11: the number average molecular weight of the polyetheretherketone is 20000 g / mol to 50000 g / mol; the mass percentage of the sodium borohydride solution is 1wt%-5wt%, and the solvent in the solution is dimethyl sulfoxide; the first alcohol solution is one or more of methanol, ethanol, propanol, isopropanol, butanol, and isobutanol; the inorganic acid solution is a 0.2-0.8 mol / L HCl aqueous solution; the mass ratio of the polyetheretherketone to the sodium borohydride is 5-10:1-2;

[0015] In S12: the mass percentage of the hexamethylene diisocyanate solution is 3wt%-8wt%, and the solvent in the solution is a benzene solvent, such as toluene, xylene, etc.;

[0016] The mass ratio of hydroxylated polyetheretherketone, hexamethylene diisocyanate and diazabicyclooctane is 5-10:2-5:0.5-1;

[0017] The soaking reaction temperature in the inert atmosphere is 10-30°C and the soaking reaction time is 2-5 days;

[0018] In S13: the solvent in the dioxane alkaline solution is a 0.2-0.8 mol / L sodium hydroxide aqueous solution;

[0019] The mass ratio of isocyanate polyetheretherketone, dioxane and sodium hydroxide is 5-10:0.5-1:0.5-1;

[0020] The reaction temperature of the isocyanate polyetheretherketone in the dioxane alkaline solution is 10-30° C. and the reaction time is 3-8 hours.

[0021] Further, the method for obtaining the hydroxyl-modified boron nitride described in S1 is: in an inert atmosphere in a tube furnace, BN powder is treated with water vapor in the range of 800-900° C. for 2-5 hours, then washed, ultrasonically dispersed multiple times, filtered and freeze-dried to obtain hydroxyl-modified boron nitride;

[0022] The BN powder is h-BN, and its flake diameter is 80nm-200nm and thickness is 0.7nm-2nm; the mass percentage of hydroxyl in the hydroxyl-modified boron nitride is 0.1wt%-1wt%.

[0023] Further, in S1: the mass ratio of the amino polyetheretherketone to the hydroxyl-modified boron nitride is 10:1-5;

[0024] In S2: the oxidant is selected from one or more of FeCl3, CuCl2; the mass ratio of the composite fine powder, the thiophene monomer and the oxidant is 50-200:50-150:0.1-1; the reaction temperature of the oxidative polymerization is 25-60°C, and the reaction time is 0.5-12h; the proportion of the composite fine powder in the conjugated polythiophene-polyetheretherketone composite material is 20wt%-30wt%.

[0025] Aminated polyetheretherketone and hydroxyl-modified boron nitride chemically bond the amino group on polyetheretherketone with the hydroxyl group on boron nitride under high-temperature melting conditions to achieve uniform compounding of BN-OH and PEEK-NH2. In the subsequent oxidative polymerization of thiophene monomers by oxidants such as FeCl3 and CuCl2, the π electron cloud of the thiophene monomer overlaps with the π electron cloud of the adjacent monomer, and uniform oxidative polymerization forms a conjugated structure on the surface of the BN-OH / PEEK-NH2 composite fine powder, enhancing the light absorption performance and more effectively utilizing sunlight for photocatalytic sterilization.

[0026] Furthermore, the particle sizes of the composite fine powder and the conjugated polythiophene-polyetheretherketone composite material are less than 50 μm.

[0027] Furthermore, the parameters of the electrostatic spraying in S3 are as follows: electrostatic voltage 60-80 kV, electrostatic current 20-30 μA, powder supply pressure 0.05-0.15 MPa, spraying distance 0.2 m, and the powder spraying amount of the conjugated polythiophene composite material 100-200 g / min.

[0028] Furthermore, the heat treatment temperature in S3 is 360-390°C and the treatment time is 10-30min; the quenching and solidification is to immerse the intermediate product after the heat treatment directly in an ice-water mixture below 5°C for 3-5min.

[0029] Another aspect of the present invention provides a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating prepared by the above preparation method.

[0030] Beneficial technical effects:

[0031] The hydroxyl-modified boron nitride (BN-OH) with photocatalytic ability is melt-blended with amino-PEEK to produce chemical bonding to form BN-OH / PEEK-NH2 composite fine powder material, and then the BN-OH / PEEK-NH2 composite fine powder and thiophene monomer are oxidatively polymerized under the action of an oxidant to synthesize a polythiophene / BN-OH / PEEK-NH2 conjugated composite material in situ;

[0032] The chemical bonding between BN-OH and PEEK-NH2 can make BN evenly dispersed in the PEEK matrix and better anchored with PEEK to prevent the subsequent coating from migrating during the friction process and causing a decrease in wear resistance;

[0033] The in-situ synthesized conjugated polythiophene / BN-OH / PEEK-NH2 composite material of the present invention has a conjugated conductive structure with π-π interaction between the benzene ring and the thiophene ring in the polythiophene molecular structure, and the conjugated polythiophene is evenly distributed and bonded on the surface of the BN-OH / PEEK-NH2 composite material. After composite, it has a wider light absorption range. Under light, the conductive conjugated polythiophene acts as a photoelectrode to help capture and transfer light energy. Under the action of the semiconductor boron nitride as a catalyst, the photoelectric effect reacts rapidly, and sunlight can be more effectively used for photocatalytic sterilization, and the photocatalytic reaction can be driven more quickly.

[0034] The present invention uses an in-situ synthesized polythiophene / BN-OH / PEEK-NH2 conjugated composite material and electrostatically sprays it onto the surface of a substrate, and then melts and solidifies it to make the coating evenly distributed. The resulting coating has excellent high-temperature tolerance and can still maintain stable performance under high-temperature environments. The coating material of the present invention has a continuous use temperature of up to 260°C and can even work for a short period of time at a temperature of 330°C, and has good thermal stability; it also has excellent wear resistance and has a relatively low friction coefficient at room temperature and high temperature. DETAILED DESCRIPTION

[0035] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. 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.

[0036] Unless otherwise specifically stated, the numerical value set forth in these embodiments does not limit the scope of the present invention. The technology and method known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the technology and method should be considered as a part of the specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary, rather than as a limitation. Therefore, other examples of exemplary embodiments may have different values.

[0037] The experimental methods in the following examples without specifying specific conditions are usually measured in accordance with national standards; if there is no corresponding national standard, the method is carried out in accordance with the general standard requirements or general methods.

[0038] Preparation Example 1

[0039] This case is the preparation of amino polyetheretherketone:

[0040] 100 g of PEEK powder (particle size 15-20 μm, number average molecular weight 20000 g / mol to 50000 g / mol) was immersed in 1000 g of a solution of dimethyl sulfoxide containing NaBH4 (the content of NaBH4 was 2 wt%), dried at 120°C for 3 hours, and then rinsed with methanol, water, 0.5 mol / L HCl, water, and ethanol in sequence to obtain hydroxylated PEEK (abbreviated as PEEK-OH);

[0041] 100 g of PEEK-OH was immersed in 1000 g of a toluene solution containing hexamethylene diisocyanate (the content of hexamethylene diisocyanate was 5 wt%), and 10 g of diazabicyclooctane was added as a catalyst, and the mixture was immersed at 20° C. under an argon atmosphere for 3 days, and then rinsed with toluene and acetone in sequence to obtain isocyanate-modified polyetheretherketone (abbreviated as PEEK-NCO) powder;

[0042] 100 g of PEEK-NCO was treated with 500 mL of a dioxane alkaline solution (NaOH content: 0.5 mol / L, dioxane content: 1.8 wt%) at 20° C. for 5 hours, and then washed with water and acetone to obtain amino polyetheretherketone (abbreviated as PEEK-NH2).

[0043] The amino content of PEEK-NH2 obtained in this case is 0.046wt%.

[0044] Preparation Example 2

[0045] This case is the preparation of hydroxyl-modified boron nitride:

[0046] Hexagonal boron nitride (h-BN, flake diameter 80-200nm, thickness 0.7-2nm) was vacuum dried at 60°C in a quartz ark, placed in the center of a tube furnace, and water vapor (flow rate 0.2L / min) was introduced. The tube furnace was gradually heated from room temperature to 830°C at a heating rate of 10°C / min, and kept warm for 3 hours under argon gas flow (flow rate 1L / min). After the reaction was completed, it was cooled and the powder obtained by repeated washing and filtration was ultrasonically dispersed in deionized water 3 times, filtered and freeze-dried to obtain hydroxyl-modified boron nitride (abbreviated as BN-OH).

[0047] The hydroxyl content of the BN-OH obtained in this case is 2wt%.

[0048] Example 1

[0049] A method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating comprises the following steps:

[0050] S1. The PEEK-NH2 of Preparation Example 1 and the BN-OH of Preparation Example 2 were mixed in a mass ratio of 5:2, and then melt-blended using a twin-screw extruder. The specific parameters were as follows: zone 1 280-360°C, zone 2 320-380°C, zone 3 to zone 6 350-380°C, zone 7 350-380°C, die temperature 350-380°C, screw speed 20-40rpm, feeding frequency 10-15Hz; die size 5mm, extrusion, granulation, the particles were crushed and refined to a particle size of 40μm, to obtain BN-OH / PEEK-NH2 composite fine powder;

[0051] S2, dispersing 70g of BN-OH / PEEK-NH2 composite fine powder and 50g of thiophene monomer in 1.5L of a mixed solution of deionized water and ethanol (the volume proportion of anhydrous ethanol is 50vol%) and stirring until a uniform suspension is obtained;

[0052] Disperse 100 mg FeCl3 in 500 mL water and stir evenly to obtain an oxidant solution;

[0053] Under continuous stirring, the oxidant solution is added dropwise to the above suspension for oxidative polymerization. After the addition is completed, the reaction is continued at room temperature for 3 hours. After the reaction is completed, it is filtered and washed, and placed in a vacuum oven at 60°C for 24 hours to obtain an in-situ synthesized conjugated polythiophene-polyetheretherketone composite material (i.e., polythiophene / BN-OH / PEEK-NH2 conjugated composite material), abbreviated as CPTH / BN-OH / PEEK-NH2 composite material (CPTH accounts for about 41.6wt%, PEEK-NH2 accounts for about 41.7wt%, and BN-OH accounts for about 16.7wt%), which is crushed and refined to a particle size of 40μm;

[0054] S3. After the surface of the stainless steel pipe is cleaned, the surface of the substrate is sandblasted with a sandblasting machine. The mesh number of the diamond sand (silicon carbide) used is 80 mesh to remove the oxide layer on the surface of the substrate, increase the surface roughness of the substrate, and enhance the adhesion of the coating;

[0055] Then 100 g of 40 μm dried CPTH / BN-OH / PEEK-NH2 composite was electrostatically sprayed onto the surface of the pretreated stainless steel pipe (the surface area of ​​the substrate was about 1 m 2 ), set the parameters of the electrostatic spraying equipment: electrostatic voltage 70kV, electrostatic current 25μA, powder supply pressure 0.10MPa, spraying distance 0.2m, powder spraying amount 150g / min;

[0056] The sprayed intermediate part is placed in a heating furnace and heat treated at 380°C for 20 minutes. After the heat treatment, it is directly quenched in an ice-water mixture below 5°C to obtain a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating.

[0057] The coating material obtained in Example 1 was subjected to thermogravimetric analysis. The temperature was increased from room temperature to 800°C in an air atmosphere at a rate of 10°C / min. The results showed that the weight loss rate of the coating material at 330°C was only about 1%, which is much lower than the generally considered material failure weight loss standard of 5%. This indicates that the degree of thermal decomposition of the material at 330°C is very small, and it has good thermal stability. The coating has good high-temperature stability.

[0058] Example 2

[0059] A method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating comprises the following steps:

[0060] S1. The PEEK-NH2 of Preparation Example 1 and the BN-OH of Preparation Example 2 were mixed in a mass ratio of 5:1, and then melt-blended using a twin-screw extruder. The specific parameters were as follows: zone 1 280-360°C, zone 2 320-380°C, zone 3 to zone 6 350-380°C, zone 7 350-380°C, die temperature 350-380°C, screw speed 20-40rpm, feeding frequency 10-15Hz; die size 5mm, extrusion, granulation, the particles were crushed and refined to a particle size of 40μm, to obtain BN-OH / PEEK-NH2 composite fine powder;

[0061] S2, dispersing 120g of BN-OH / PEEK-NH2 composite fine powder and 100g of thiophene monomer in 1.5L of a mixed solution of deionized water and ethanol (the volume proportion of anhydrous ethanol is 50vol%) and stirring until a uniform suspension is obtained;

[0062] Disperse 250 mg FeCl3 in 500 mL water and stir evenly to obtain an oxidant solution;

[0063] Under continuous stirring, the oxidant solution is added dropwise to the above suspension for oxidative polymerization. After the addition is completed, the reaction is continued at room temperature for 6 hours. After the reaction is completed, it is filtered and washed, and placed in a vacuum oven at 60°C for 24 hours to obtain an in-situ synthesized conjugated polythiophene-polyetheretherketone composite material (i.e., polythiophene / BN-OH / PEEK-NH2 conjugated composite material), abbreviated as CPTH / BN-OH / PEEK-NH2 composite material (CPTH accounts for about 45.4wt%, PEEK-NH2 accounts for about 45.5wt%, and BN-OH accounts for about 9.1wt%), which is crushed and refined to a particle size of 40μm;

[0064] S3. After the surface of the aluminum alloy plate is cleaned, the surface of the substrate is sandblasted with a sandblasting machine. The mesh number of the diamond sand (silicon carbide) used is 50 mesh, so as to remove the oxide layer on the surface of the substrate, improve the surface roughness of the substrate, and enhance the adhesion of the coating;

[0065] Then 200 g of 40 μm dried CPTH / BN-OH / PEEK-NH2 composite was electrostatically sprayed onto the surface of the pretreated aluminum alloy plate (the surface area of ​​the substrate was about 1.5 m 2 ), set the parameters of the electrostatic spraying equipment: electrostatic voltage 60kV, electrostatic current 30μA, powder supply pressure 0.15MPa, spraying distance 0.2m, powder spraying amount 200g / min;

[0066] The sprayed intermediate part is placed in a heating furnace and heat treated at 390°C for 15 minutes. After the heat treatment, it is directly quenched in an ice-water mixture below 5°C to obtain a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating.

[0067] Example 3

[0068] A method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating comprises the following steps:

[0069] S1. The PEEK-NH2 of Preparation Example 1 and the BN-OH of Preparation Example 2 were mixed in a mass ratio of 10:1, and then melt-blended using a twin-screw extruder. The specific parameters were as follows: zone 1 280-360°C, zone 2 320-380°C, zone 3 to zone 6 350-380°C, zone 7 350-380°C, die temperature 350-380°C, screw speed 20-40rpm, feeding frequency 10-15Hz; die size 5mm, extrusion, granulation, the particles were crushed and refined to a particle size of 40μm, to obtain BN-OH / PEEK-NH2 composite fine powder;

[0070] S2, dispersing 165g of BN-OH / PEEK-NH2 composite fine powder and 150g of thiophene monomer in 1.5L of a mixed solution of deionized water and ethanol (the volume proportion of anhydrous ethanol is 50vol%) and stirring until a uniform suspension is obtained;

[0071] Disperse 300 mg of FeCl3 in 500 mL of water and stir evenly to obtain an oxidant solution;

[0072] Under continuous stirring, the oxidant solution is added dropwise to the above suspension for oxidative polymerization. After the addition is completed, the reaction is continued at room temperature for 12 hours. After the reaction is completed, it is filtered and washed, and placed in a vacuum oven at 60°C for 24 hours to obtain an in-situ synthesized conjugated polythiophene-polyetheretherketone composite material (i.e., polythiophene / BN-OH / PEEK-NH2 conjugated composite material), abbreviated as CPTH / BN-OH / PEEK-NH2 composite material (CPTH accounts for about 47.6wt%, PEEK-NH2 accounts for about 47.6wt%, and BN-OH accounts for about 4.8wt%), which is crushed and refined to a particle size of 40μm;

[0073] S3. After the surface of the copper alloy pipe is cleaned, the surface of the substrate is sandblasted with a sandblasting machine. The mesh number of the diamond sand (silicon carbide) used is 50 mesh to remove the oxide layer on the surface of the substrate, increase the surface roughness of the substrate, and enhance the adhesion of the coating;

[0074] Then 300 g of 40 μm dried CPTH / BN-OH / PEEK-NH2 composite was electrostatically sprayed onto the surface of the pretreated copper alloy tube (the surface area of ​​the substrate was about 2 m 2 ), set the parameters of the electrostatic spraying equipment: electrostatic voltage 80kV, electrostatic current 20μA, powder supply pressure 0.1MPa, spraying distance 0.2m, powder spraying amount 100g / min;

[0075] The sprayed intermediate part is placed in a heating furnace and heat treated at 370°C for 30 minutes. After the heat treatment, it is directly quenched in an ice-water mixture below 5°C to obtain a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating.

[0076] Comparative Example 1

[0077] The preparation process of the coating in this case is the same as that in Example 1, except that:

[0078] In S1, hexagonal boron nitride (not hydroxyl-modified, obtained by ultrasonic dispersion in deionized water three times, filtration and freeze-drying) and PEEK (not amino-modified) are melt-blended; the composite material obtained in the subsequent S2 step is recorded as CPTH / BN / PEEK composite material.

[0079] Comparative Example 2

[0080] The preparation process of the coating in this case is the same as that in Example 1, except that:

[0081] In S1, hexagonal boron nitride (not modified with hydroxyl groups, obtained by ultrasonic dispersion in deionized water three times, filtration and freeze-drying) is melt-blended with the amino PEEK of Preparation Example 1; the composite material obtained in the subsequent step S2 is recorded as CPTH / BN / PEEK-NH2 composite material.

[0082] Comparative Example 3

[0083] The preparation process of the coating in this case is the same as that in Example 1, except that:

[0084] In S1, the hydroxyl-modified boron nitride of Preparation Example 2 is melt-blended with PEEK (not aminated); the composite material obtained in the subsequent step S2 is recorded as CPTH / BN-OH / PEEK composite material.

[0085] Comparative Example 4

[0086] The preparation process of the coating in this case is as follows: conjugated polythiophene, BN-OH of Preparation Example 2, and PEEK-NH2 of Preparation Example 1 are configured according to the ratio in the S2 composite material of Example 1. After the three are evenly mixed, a twin-screw extruder is used for melt blending, extrusion and granulation. After the particle size is refined to 40 μm, the coating is prepared by step 3 of Example 1.

[0087] Comparative Example 5

[0088] The preparation process of the coating in this case is as follows: conjugated polythiophene and PEEK-NH2 of Preparation Example 1 (configured according to the proportion of PEEK-NH2 in the S2 composite material of Example 1) are directly mixed evenly, and then melt-blending and extruding granulation are performed using a twin-screw extruder. After the particle size is refined to 40 μm, the coating is prepared using Step 3 of Example 1.

[0089] Comparative Example 6

[0090] The preparation process of the coating in this case is: electrostatic spraying is performed using the BN-OH / PEEK-NH2 composite material of step S1 of Example 1.

[0091] Test Case

[0092] Antibacterial property, friction coefficient and coating adhesion test results are shown in Table 1 below.

[0093] Table 1 Coating properties of each case

[0094]

[0095]

[0096] As can be seen from Table 1, the coating obtained by electrostatically spraying the in-situ synthesized polythiophene / BN-OH / PEEK-NH2 conjugated composite material onto the surface of the substrate has excellent wear resistance at room temperature and high temperature, excellent antibacterial property, and good adhesion.

[0097] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating, characterized in that: The steps include: S1, mixing amino polyetheretherketone and hydroxyl-modified boron nitride in proportion and then melt blending, extruding, granulating and refining the particle size in sequence to obtain composite fine powder; S2, oxidatively polymerizing the composite fine powder and thiophene monomer under the action of an oxidant to in-situ synthesize a conjugated polythiophene-polyetheretherketone composite material; S3, electrostatically spraying the conjugated polythiophene composite material onto the pretreated surface of the metal substrate, and subjecting it to heat treatment, quenching and curing to form a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating.

2. The method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating according to claim 1, characterized in that: The method for obtaining the amino polyetheretherketone described in S1 is: S11, immersing the polyetheretherketone in a sodium borohydride solution, then drying, and then washing with an alcohol solution, water, an inorganic acid solution, water, and an alcohol solution in sequence to obtain a hydroxylated polyetheretherketone; introducing amino groups into the PEEK molecular structure through chemical modification to improve biocompatibility and reactivity; S12, the hydroxylated polyetheretherketone is immersed in a hexamethylene diisocyanate solution with diazabicyclooctane as a catalyst in an inert atmosphere for reaction to obtain isocyanated polyetheretherketone; Treat BN powder with high-temperature steam to form a hydroxylated surface; S13, placing the isocyanate polyetheretherketone in a dioxane alkaline solution for reaction, washing and drying to obtain an amino polyetheretherketone, wherein the mass percentage of amino groups in the obtained amino polyetheretherketone is about 0.1wt%-1wt%.

3. The method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating according to claim 2, characterized in that: In S11: the number average molecular weight of the polyetheretherketone is 20000 g / mol to 50000 g / mol; the mass percentage of the sodium borohydride solution is 1wt%-5wt%, and the solvent in the solution is dimethyl sulfoxide; the first alcohol solution is one or more of methanol, ethanol, propanol, isopropanol, butanol, and isobutanol; the inorganic acid solution is a 0.2-0.8 mol / L HCl aqueous solution; the mass ratio of the polyetheretherketone to the sodium borohydride is 5-10:1-2; In S12: the mass percentage of the hexamethylene diisocyanate solution is 3wt%-8wt%, and the solvent in the solution is a benzene solvent; The mass ratio of hydroxylated polyetheretherketone, hexamethylene diisocyanate and diazabicyclooctane is 5-10:2-5:0.5-1; The soaking reaction temperature in the inert atmosphere is 10-30°C and the soaking reaction time is 2-5 days; In S13: the solvent in the dioxane alkaline solution is a 0.2-0.8 mol / L sodium hydroxide aqueous solution; The mass ratio of isocyanate polyetheretherketone, dioxane and sodium hydroxide is 5-10:0.5-1:0.5-1; The reaction temperature of the isocyanate polyetheretherketone in the dioxane alkaline solution is 10-30° C. and the reaction time is 3-8 hours.

4. The method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating according to claim 1, characterized in that: The method for obtaining the hydroxyl-modified boron nitride described in S1 is: in an inert atmosphere in a tube furnace, BN powder is treated with water vapor at 800-900° C. for 2-5 hours, then washed, ultrasonically dispersed multiple times, filtered and freeze-dried to obtain the hydroxyl-modified boron nitride; The BN powder is h-BN, and its flake diameter is 80nm-200nm and thickness is 0.7nm-2nm; the mass percentage of hydroxyl in the hydroxyl-modified boron nitride is 0.1wt%-1wt%.

5. The method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating according to claim 1, characterized in that: In S1: the mass ratio of the amino polyetheretherketone to the hydroxyl-modified boron nitride is 10:1-5; In S2: the oxidant is selected from one or more of FeCl3, CuCl2; the mass ratio of the composite fine powder, the thiophene monomer and the oxidant is 50-200:50-150:0.1-1; the reaction temperature of the oxidative polymerization is 25-60°C, and the reaction time is 0.5-12h; the proportion of the composite fine powder in the conjugated polythiophene-polyetheretherketone composite material is 20wt%-30wt%.

6. The method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating according to claim 1, characterized in that: The particle sizes of the composite fine powder and the conjugated polythiophene-polyetheretherketone composite material are less than 50 μm.

7. The method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating according to claim 1, characterized in that: The parameters of the electrostatic spraying in S3 are as follows: electrostatic voltage 60-80 kV, electrostatic current 20-30 μA, powder supply pressure 0.05-0.15 MPa, spraying distance 0.2 m, and the powder spraying amount of the conjugated polythiophene composite material 100-200 g / min.

8. The method for preparing a conjugated polythiophene-polyetheretherketone-based highly antibacterial coating according to claim 1, characterized in that: The heat treatment temperature in S3 is 360-390° C. and the treatment time is 10-30 min. The quenching and curing is to immerse the intermediate product after the heat treatment directly in an ice-water mixture below 5° C. for 3-5 min.

9. A conjugated polythiophene-polyetheretherketone-based highly antibacterial coating prepared according to the preparation method according to any one of claims 1 to 8.

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