CN1706887B - A carbon nanotube-polymer composite material used in blood environment and its preparation method and application - Google Patents

Abstract

The invention discloses a carbon nanotube-polymer composite material used in a blood environment, including carbon nanotubes and a high molecular polymer, wherein the carbon nanotubes are uniformly dispersed in the high molecular polymer through liquid phase co-precipitation, And precisely control the addition of carbon nanotubes at 1-6% by weight; the present invention also provides a preparation method of the above-mentioned materials, which is to dissolve the carbon nanotubes in a co-solvent after making the carbon nanotubes hydrophilic, and then mix them with the high molecular polymer solution After mixing, a trigger is added for co-precipitation. The carbon nanotube-polymer composite material provided by the invention, the carbon nanotubes are uniformly dispersed in the composite material, can be dissolved in an organic solvent again, and can be used as a coating material on the surface of a medical device or an implantable prosthesis used in a blood environment , or used as raw materials in the manufacture of artificial tissues, organs or interventional devices.

Description

A carbon nanotube-polymer composite material used in blood environment and its preparation method and application

technical field

The invention relates to a carbon nanotube-polymer composite material used in the field of biomedicine, and also relates to its preparation method and application.

Background technique

Carbon nanotubes are a class of tubular carbon materials with a perfect graphite structure, and their diameters generally range from a few nanometers to tens of nanometers. Carbon nanotubes have excellent electrical conductivity, electromagnetic properties, and excellent mechanical properties, as well as good biocompatibility. Its comprehensive excellent properties have aroused great research interest in the field of biomedicine.

However, due to the huge specific surface area of carbon nanotubes, there is a very strong agglomeration between them, so it is difficult for carbon nanotubes to disperse in water, organic solvents, and polymer matrices. Research on the composite of carbon nanotubes and organic polymer matrix, the polymers involved include epoxy resin, nylon, polyacrylate, polyurethane and so on. In the preparation of these composite materials, how to uniformly disperse carbon nanotubes into the polymer matrix is the key technology. The existing dispersion methods mainly include: (1) dispersing carbon nanotubes into the polymer matrix through ultrasonic resonance or strong mechanical stirring. In the polymer solution, the existing problem is that it is still difficult to completely and evenly disperse the carbon nanotubes in the polymer solution by means of ultrasonic oscillation or mechanical strong blending, and the stability of the formed solution system is poor. Generally, the amount of carbon nanotubes added is 1- At 2%, it reaches saturation, and the carbon nanotubes form aggregates and cannot be dispersed (such as the document Phys Chem B 2002, 106, 2210). (2) Some organic molecules or polymers are grafted on the surface of carbon nanotubes, (such as the literature Ya-ping Sun, et al., Functionalized Carbon Nanotubes: Properties and Applications.Acc.Chem.Res.2002, 35, 1096- 1104), the grafted macromolecules are PPEI, PVK-PS, PS ₁ , PEG, PVA-VA, etc., which increase the dispersion of carbon nanotubes in solvent media; this type of method introduces other substances in the system; (3 ) disperse the carbon nanotubes into the monomer solution by adding surfactant or coupling agent, and then initiate the polymerization process to form carbon nanotube-polymer composite materials, (such as literature Harry J. et al., SWNT-filled Thermal plastic and Elastic composite prepared by miniemulsion polymerization.Nanoletters 2(8), 2002); it can be seen that the composite material formed in this way still has the problems of method (1) to a certain extent, and other substances such as surfactants and initiators are introduced , and need to go through a relatively complicated polymerization reaction process.

The research on the application of carbon nanotubes in the field of biomedicine is still relatively small so far. The main application research of carbon nanotubes involves the following aspects, including (1) using carbon nanotubes as probes for biological imaging; (2) using carbon nanotubes as probes for biological imaging; Surface modification and functionalization of carbon nanotubes to prevent non-specific binding and recognition of specific protein molecules on the surface of protein molecules; (3) used for in vitro growth of nerve cells after modification of biomolecules; and (4) carbon nanotubes Biocompatibility studies.

When carbon nanotube polymer composite materials are applied to specific biological systems (such as implants of the cardiovascular system, artificial organs, interventional catheters, blood circulation pipelines, etc.), in addition to ensuring that the carbon nanotube polymer composite system In addition to the dispersibility and stability of the material, it is also particularly required that the material should keep its chemical composition as pure as possible, and try not to introduce other components that have uncertain effects on the biological system into the material; The addition amount of the tube and can control the addition amount of the carbon nanotube. At present, none of the existing composite methods and their products can meet this requirement. On the other hand, in many cases, biomaterials need to be applied to the surface modification of medical devices or implantable prostheses in the form of coating and film formation, or to manufacture implantable devices of various complex shapes by solution casting, This requires that the obtained carbon nanotube-polymer composite material can be formulated into a solution with a certain concentration and used in a solution state; however, the composite products developed by existing methods basically cannot meet this requirement.

Contents of the invention

The purpose of the present invention is to provide carbon nanotube-polymer composite material used in blood contact environment.

The carbon nanotube-polymer composite material used in the blood environment provided by the present invention includes carbon nanotubes and high molecular polymers, and is characterized in that the carbon nanotubes are uniformly dispersed in the polymer through liquid phase co-precipitation In the polymer, and precisely control the addition of carbon nanotubes at 1-6% by weight, wherein the high molecular polymer is selected from polyurethane, polyvinyl chloride, polyester, polylactic acid and lactic acid-glycolic acid copolymer kind of.

Another object of the present invention is to provide a method for preparing the above-mentioned carbon nanotube-polymer composite material.

The preparation method of the carbon nanotube-polymer composite material provided by the present invention comprises the following steps:

1) Carry out surface treatment to carbon nanotube, form carboxylic acid group on the surface of carbon nanotube, obtain hydrophilic carbon nanotube;

2) Select two or more solvents with different polarities to form a co-solvent, so that the water-soluble carbon nanotubes obtained in step 1) are evenly dispersed in the co-solvent;

3) Dissolving the high molecular polymer in an organic solvent, mixing the carbon nanotube-co-solvent solution obtained in step 2) with the high molecular polymer-organic solvent solution to form a carbon nanotube-high molecular polymer- solvent system;

4) adding a triggering agent to the carbon nanotube-polymer-solvent system, so that the carbon nanotube and the polymer co-precipitate to obtain a precipitate;

5) The non-volatile solvent in the precipitate in step 4) is removed by a replacement method to obtain a carbon nanotube-polymer composite.

In the above method, the surface treatment of the carbon nanotubes in step 1) means that the carbon nanotubes are ultrasonically treated at a frequency of 10-80KHz for 10-120 minutes with a mixed acid, and the mixed acid can be hydrochloric acid, nitric acid, sulfuric acid, acetic acid A mixture of two or more of , butyric acid, and maleic acid.

Step 2) The co-solvent is a mixture of two or more selected from water, tetrahydrofuran, dioxane, methanol, ethanol, butanol, acetone, butanone, methyl acetate, and ethyl acetate, wherein Water, methanol, ethanol, tetrahydrofuran are preferred.

Step 4) The triggering agent is water, methanol, ethanol, butanol, acetone or butanone, preferably water, methanol, ethanol, and the temperature during co-precipitation is 0-60°C.

The replacement method in step 5) is to select a solvent with a low boiling point, strong volatility, miscible with the organic solvent and insoluble with the polymer in step 3) to replace the non-volatile organic solvent in the composite material.

Another object of the present invention is to provide the application of the above-mentioned carbon nanotube-polymer composite material in an environment in direct contact with blood.

The application is first of all the application of the above-mentioned carbon nanotube-polymer composite material as a coating material on the surface of medical devices or implanted prostheses used in the blood environment, or as a raw material in the manufacture of artificial tissues, organs or interventional devices application. In the application, the carbon nanotube-polymer composite material needs to be dissolved in a solvent and then formulated into a solution as a coating material, or through mold casting, extrusion or injection molding; the solvent is selected from tetrahydrofuran, dioxane, One of dimethylformamide, dimethylacetamide, and methyl ethyl ketone.

The present invention proposes a new preparation method of carbon nanotube-polymer composite material, so that carbon nanotube and polymer material form a composite in a co-solvent system, carbon nanotubes are uniformly dispersed in the composite system, and the composite The amount of carbon nanotubes added in the medium can vary from 1-6% (weight percent), and the amount of carbon nanotubes added can be precisely controlled; the compound can be formulated into a solution as required, cast into a film or coated on a base material, It can also be extruded directly or blended with other materials as a masterbatch.

Description of drawings

FIG. 1 is an electron micrograph of carbon nanotubes used in the present invention.

Fig. 2A is an experimental diagram of the stability of the carbon nanotube-polyurethane-co-solvent system during the preparation process of the present invention.

Fig. 2B is a diagram of the stability experiment of the carbon nanotube aqueous solution-polyurethane-tetrahydrofuran solution system in the control experiment.

Fig. 3-A is a scanning electron micrograph of the cross-section of the carbon nanotube-polyurethane composite material prepared in the present invention.

Fig. 3-B is the DSC spectrum of the carbon nanotube-polyurethane composite material prepared in the present invention.

Fig. 4-A is the carbon nanotube-polyurethane composite material prepared in the present invention.

Fig. 4-B is the morphological photograph of the 5% tetrahydrofuran solution of the carbon nanotube-polyurethane composite material prepared by the present invention and the comparison sample solution, wherein, 1# is the composite material tetrahydrofuran solution of the present invention, and 2# is the carbon nanotube in polyurethane tetrahydrofuran The solution after ultrasonic dispersion in the solution, 3# is polyurethane solution.

Figure 4-C is an optical microscope photo (25×16) corresponding to the solution in Figure 4-B.

Fig. 5 is the IABP balloon catheter made of the carbon nanotube-polyurethane composite material prepared by the present invention.

Figure 6-A is an electron micrograph of platelets (human blood) adsorbed on the surface of polyurethane.

Fig. 6-B is an electron microscope image of platelets (human blood) adsorbed on the surface of the carbon nanotube-polyurethane composite material prepared in the present invention.

Fig. 7-A is the platelet (sheep blood) electron microscope image adsorbed on the polyurethane surface;

Fig. 7-B is an electron microscope image of platelets (sheep blood) adsorbed on the surface of the carbon nanotube-polyurethane composite material prepared in the present invention.

Figure 8 is the positive rate of GP IIb/IIIa on the platelet membrane surface in platelet-rich plasma after contacting the material surface for 15 minutes.

Fig. 9 is the hemolysis rate of the carbon nanotube-polyurethane composite material prepared in the present invention.

Fig. 10 shows pellets and other moldings made of the carbon nanotube-polyurethane composite material prepared in the present invention.

Detailed ways

The present invention is described in detail below from several aspects.

The invention firstly provides a method for preparing carbon nanotube-polymer composite material in a co-solvent system. The present invention is characterized in that (1) no organic molecules or macromolecules are introduced on the surface of the carbon nanotubes, and the surface-treated carbon nanotubes only have oxygen-containing groups such as carboxyl, hydroxyl, and etheroxy groups; The monomer starts to carry out the polymer polymerization reaction, and the co-solvent solution of carbon nanotubes can be directly mixed with various polymer solutions to obtain a composite product with uniform dispersion of carbon nanotubes; (3) the amount of carbon nanotubes added in the composite material can be within 1-6% (weight percent) change, and can precisely control the addition of carbon nanotubes; (4) The composite material can be formulated into a solution as required, cast into a film or coated on the base material, and can also be directly extruded Or it can be used as a masterbatch and blended with other materials for extrusion.

The method of the present invention is that after the carbon nanotubes are subjected to water-soluble treatment, they are evenly dispersed in a co-solvent composed of two or more solvents with different polarities, and then mixed evenly with the high molecular polymer that has been dissolved in an organic solvent, A stable co-solution system is formed, and co-precipitation occurs through the action of a trigger to obtain a carbon nanotube-polymer composite material with excellent dispersibility. The method ensures that the carbon nanotubes can be uniformly dispersed in the solvent by selecting a suitable co-solvent, thereby obtaining a product through liquid phase co-precipitation, and ensuring that the carbon nanotubes in the composite product can be uniformly dispersed in the polymer. The dispersibility of carbon nanotubes in the composite system is one of the characteristics of the composite material of the present invention, and Experiment 2 concretely verified the characteristics of the dispersibility of the present invention.

In the present invention, the carbon nanotubes used are multi-walled carbon nanotubes, the pipe diameter is 30-50nm, and the length>2μm, referring to Fig. 1, the high molecular polymer that can be compounded with carbon nanotubes can be polyurethane, polyvinyl chloride, Any one of polycarbonate, epoxy resin, polyester, polylactic acid, polyglycolic acid, lactic acid-glycolic acid copolymer, preferably polyurethane.

In the method of the present invention, the surface treatment method for carbon nanotubes may include: ultrasonically oscillating carbon nanotubes with an acid solution mixed in a certain proportion at an appropriate temperature. In the embodiment of the present invention, the method of ultrasonic treatment is adopted, and the carbon nanotubes are ultrasonically treated with a mixed acid at a frequency of 10-80KHz for 10-120 minutes. The mixed acid can be hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, ma A mixture of two or more acids.

In the method of the present invention, the solvent for dispersing water-soluble carbon nanotubes can be two or more of water, tetrahydrofuran, dioxane, methanol, ethanol, butanol, acetone, butanone, methyl acetate, ethyl acetate The mixture of two or more forms a co-solvent, among which water, methanol, ethanol, tetrahydrofuran, and dioxane are preferred.

In the method of the present invention, the triggering agent for coprecipitation is water, methanol, ethanol, butanol, acetone or butanone, preferably water, methanol, ethanol, and the temperature for coprecipitation is 0-60°C.

In the method of the present invention, there are non-volatile solvents in the co-precipitation product, and these solvents need to be removed during the post-treatment, and a replacement method can be used.

For the specific preparation method of the present invention, refer to Examples 1 and 2.

Embodiment 1. Preparation of carbon nanotube-polyurethane composite material

(1) Weigh 0.25 g of carbon nanotubes into a round bottom flask, and add 40 ml of 2:1 concentrated sulfuric acid/concentrated nitric acid. Ultrasonic treatment at 25KHz for 10 minutes; (2), dilute with a large amount of water and use a filter membrane with a pore size of 100nm to filter and rinse to neutrality, and dry; (3), add 90 mg of carbon nanotubes after processing to 60 milliliters of 60 % in methanol aqueous solution; (4), prepare 60 milliliters of dioxane solutions of 5% polyurethane; (5), slowly join (3) in (4), obtain uniform black solution; (6 ), adding 95% ethanol dropwise to (5) until co-precipitation occurs to obtain a uniform black precipitate; (7) shear the precipitate into the size of a rice grain, and repeatedly soak the product with 95% ethanol, and then place it at 50°C Dry in a vacuum oven to obtain a carbon nanotube-polyurethane composite material. In this example, in the whole composite system, the added amount of carbon nanotubes is controlled to be 3%.

Embodiment 2. Preparation of carbon nanotube-polyvinyl chloride composite material

Using the same method as in Example 1, wherein the mixed acid is concentrated nitric acid and concentrated hydrochloric acid, the co-solvent is tetrahydrofuran, ethyl acetate, water, the high molecular polymer is polyvinyl chloride, and the trigger agent is methanol during coprecipitation. The product is carbon nanotube-polyvinyl chloride composite material. In this example, in the whole composite system, the added amount of carbon nanotubes is controlled to be 1%.

Embodiment 3, preparation of carbon nanotube-polyurethane composite material, wherein the addition of carbon nanotube is 6%

The same method as in Embodiment 1 was adopted, wherein the carbon nanotubes mixed with the polyurethane solution was 180 mg.

According to above-mentioned embodiment, carry out following experiment:

Experiment 1: Differential scanning calorimetry (DSC) analysis of the composite effect of carbon nanotubes-polymers

Under a nitrogen atmosphere, the temperature was raised at a rate of 20° C./min, and the thermal behavior of the carbon nanotube-polyurethane composite material (3% carbon nanotube addition) was recorded, with polyurethane as a reference sample. The results are shown in Figure 3B. It can be seen from the DSC spectrum that after compounding with carbon nanotubes, the original two endothermic peaks of the polyurethane material are close to each other, indicating that there is a strong interaction between carbon nanotubes and polyurethane molecules, forming a good composite system.

Experiment 2. Scanning electron microscope to observe the degree of composite and dispersion of carbon nanotubes in polymers

Place the pellets of carbon nanotube-polyurethane composite material with a carbon nanotube addition of 3% in liquid nitrogen for 30 minutes, pull it off immediately after taking it out, spray gold on the end face, and observe it under a scanning electron microscope (S-5200) The results of the cross-section morphology are shown in Figure 3A. It can be seen from the figure that there are no obvious pulled out carbon nanotubes on the cross-section, and the entire cross-section is characterized by elastic fracture. It shows that a good composite is formed between the carbon nanotube polyurethane matrix.

Experiment 3. Stability experiment of carbon nanotubes in polymer solution

In embodiment one, take the carbon nanotube-polyurethane-co-solvent sample in the step (5), be placed in the beaker and make experimental sample (1); Another carbon nanotube aqueous solution of the same concentration is directly added to 5% polyurethane tetrahydrofuran The sample in the solution is used as a control sample (2), and the changes in the solution are observed. In the control sample, polyurethane precipitates immediately, and cannot form a uniform composite with carbon nanotubes, while the experimental sample can maintain a stable uniform black solution, and no polymer appears. Precipitation and carbon nanotube aggregation phenomena, see Figures 2A and 2B. This experiment shows that the dispersion of carbon nanotubes in the polyurethane-co-solvent system is good, and the system stability is good.

Experiment 4. After the carbon nanotube-polyurethane composite material is formulated into a 5% tetrahydrofuran solution, the dispersion experiment of carbon nanotubes in the solution:

Dissolve the carbon nanotube-polyurethane composite material prepared in Example 1 in tetrahydrofuran, prepare a 5% solution, place (1) in the test tube, and simultaneously take a sample and apply it on a glass slide, and observe the dispersion of the carbon nanotube under an optical microscope Situation; In addition, the surface-treated carbon nanotubes of the same proportion are directly added to 5% polyurethane tetrahydrofuran solution, ultrasonically dispersed for 30 minutes at 25KHz, placed in (2) test tube as a control sample, and the control sample is applied to the carrier On a glass slide, the dispersion of carbon nanotubes was observed under an optical microscope. The results under the microscope are shown in Figure 4C, and it can be seen that the dispersion of carbon nanotubes in the solution in 1# test tube is significantly better than that of the contrast sample in 2# test tube; from the observation of the static test tube, see Figure 4B, (1 ) test tube keeps solution state all the time, does not appear delamination, and (2) test tube solution appears delamination phenomenon very soon, shows that composite material of the present invention can not only be reconstituted into solution and use, and the carbon nanotube in the prepared solution can still keep Better dispersibility and maintain solution stability.

At the same time, the present invention uses the methods of experiments 1 to 4 to verify the composite materials obtained in Examples 2 and 3, and also obtains the same results, which are not listed here. According to the above experiments, it is determined that with the method of the present invention, when the amount of carbon nanotubes added reaches 6%, the stability of the system during the preparation process and the stability of the solution when the composite material is reconstituted into a solution can still be guaranteed.

The present invention continues to provide the application of the carbon nanotube-polymer composite material prepared by the above method in a blood contact environment.

As mentioned earlier, when carbon nanotube polymer composites are used in blood-contact environments (such as implants in the cardiovascular system, artificial organs, interventional catheters, blood circulation lines, etc.), in addition to ensuring that the carbon nanotubes have high In addition to the dispersion and stability of the molecular composite system, it is also particularly required that the material should keep its chemical composition as pure as possible, and try not to introduce other components with uncertain effects on the biological system into the material. The carbon nanotube polymer composite material provided by the present invention does not contain other stabilizers, surfactants, and grafted polymers or organic compounds in the system, which can well meet this requirement. The application of the carbon nanotube-polymer composite material of the present invention is described below with specific examples, and these examples should not be construed as limiting the application field of the composite material.

Example 1: Application of composite materials as anticoagulant coating in blood contact environment

The composite material of the present invention is prepared into a 5% solution with tetrahydrofuran, and a test tube is made by coating and film-forming; the same method is used to make a test tube with polyurethane as a control sample. Venous blood was extracted from healthy sheep, and platelet-rich plasma (PRP) was prepared according to standard methods. Add PRP to the sample tube and incubate for 1 hour, take it out, wash off the non-adhered platelets with PBS (pH=7.4) buffer, fix, dehydrate, dry, and spray gold with standard methods, and observe the platelet adhesion under a scanning electron microscope. For the number and morphology of the platelets, see Figure 7A and Figure 7B. The results show that the number and activation degree of platelet adhesion on the surface of the carbon nanotube-polyurethane composite material (Figure 7A) are significantly lower than those of the control sample (Figure 7B).

Example 2: Use the same test tube to collect venous blood from healthy supporters, and prepare platelet suspension and plasma according to standard procedures; first use plasma to adsorb on the surface of the sample to form a plasma protein adsorption layer, and then add the platelet suspension to the test tube. Take it out after incubation for 1 hour, wash off non-adhered platelets with PBS (pH=7.4) buffer, fix, dehydrate, dry, and spray gold with standard methods, observe the number and shape of platelets adhered under a scanning electron microscope, see Fig. 6A and FIG. 6B, the results show that the platelet adhesion quantity and activation degree caused by the surface of the carbon nanotube-polyurethane composite material (FIG. 6A) are significantly lower than those of the control sample (FIG. 6B).

Example 3: Using the same test tube, collect venous blood from healthy volunteers, and prepare platelet-rich plasma (PRP) according to standard procedures. Add PRP into the sample tube and incubate for 15 minutes, take it out, mark the activated platelets with PAC-1, and analyze the activation rate of platelets in PRP by flow cytometry. The results are shown in Figure 8, which shows that the carbon nanotube-polyurethane composite material caused The activation rate of platelets was significantly reduced in PRP.

Example 4: Use the same test tube to collect venous blood from healthy supporters, mix 0.2 ml of fresh blood and 10 ml of normal saline, add it to the test tube, incubate at 37°C for 1 hour, centrifuge at 2000rpm for 10 minutes, and take the supernatant Measure the concentration of hemoglobin in the solution at 540nm, and calculate the degree of hemolysis according to the formula. The results are shown in Figure 9, which shows that the degree of hemolysis caused by the carbon nanotube-polyurethane composite material is significantly reduced.

Example 5: Making Interventional Catheters

The carbon nanotube-polyurethane composite material was prepared into 5% tetrahydrofuran solution, and the carbon nanotube-polyurethane composite material was coated on the outside of the polyurethane catheter. At the same time, the airbag was made by coating and film-forming technology. The counterpulsation effect of the airbag met the requirements of animal experiments. The manufactured airbag product is shown in Figure 5.

Example 6: Making pellets and various molding materials

The carbon nanotube-polymer composite material prepared by the present invention is a black precipitate, which can be directly made into pellets after washing and drying; it can also be dissolved in a solvent, injected into a mold, and made into various shape. Referring to Fig. 10, there are pellets, and round and square materials formed by moulds. These materials can be further used as raw materials for the preparation of medical devices, such as artificial tissues, organs or interventional devices.

Claims (10)

1. A carbon nanotube-macromolecule composite material used in the blood environment, comprising carbon nanotubes and macromolecular polymers, is characterized in that, the carbon nanotubes are multi-walled carbon nanotubes, and the pipe diameter is 30- 50nm, length > 2μm, carbon nanotubes are uniformly dispersed in the high molecular polymer through liquid phase co-precipitation, and the amount of carbon nanotubes added is precisely controlled at 1-6% by weight, wherein the high molecular polymer is polyurethane ; The liquid-phase co-precipitation comprises the steps of: 1) Carry out surface treatment to carbon nanotube, form carboxylic acid group on the surface of carbon nanotube, obtain hydrophilic carbon nanotube; 2) Selecting two or more solvents with different polarities to form a co-solvent, so that the hydrophilic carbon nanotubes obtained in step 1) are evenly dispersed in the co-solvent; 3) Dissolving the high molecular polymer in an organic solvent, mixing the carbon nanotube-co-solvent solution obtained in step 2) with the high molecular polymer-organic solvent solution to form a carbon nanotube-high molecular polymer- solvent system; 4) adding a triggering agent to the carbon nanotube-polymer-solvent system, so that the carbon nanotube and the polymer co-precipitate to obtain a precipitate; 5) The non-volatile solvent in the precipitate in step 4) is removed by a replacement method to obtain a carbon nanotube-polymer composite. 2. A method for preparing the carbon nanotube-polymer composite material according to claim 1, characterized in that it comprises all the steps of co-precipitating the carbon nanotubes in polyurethane in a liquid phase. 3. according to the preparation method of the described carbon nanotube-macromolecule composite material of claim 2, it is characterized in that, step 1) described carbon nanotube carries out surface treatment and refers to carbon nanotube is carried out at 10-80KHz frequency with mixed acid Ultrasonic treatment for 10-120 minutes, the mixed acid is a mixture of two or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid and maleic acid. 4. according to the preparation method of the described carbon nanotube-polymer composite material of claim 2, it is characterized in that, step 2) described co-solvent is selected from water, tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, butanol, A mixture of two or more of acetone, butanone, methyl acetate and ethyl acetate. 5. according to the preparation method of the described carbon nanotube-polymer composite material of claim 4, it is characterized in that, step 2) described co-solvent is selected from two or more than two kinds in water, methanol, ethanol and THF mix. . 6. according to the preparation method of the described carbon nanotube-polymer composite material of claim 2, it is characterized in that, step 4) described triggering agent is water, methanol, ethanol, butanol, acetone or butanone, temperature during co-precipitation 0-60°C. 7. The preparation method of carbon nanotube-polymer composite material according to claim 6, characterized in that, the co-solvent in step 2) is water, methanol or ethanol. 8. The carbon nanotube-macromolecular composite material of claim 1 is used as a coating material in the application of a medical device or an implanted prosthesis surface in a blood environment, or as a raw material in the manufacture of artificial tissues, organs or interventional devices on the application. 9. The application according to claim 8, characterized in that, the carbon nanotube-polymer composite material is dissolved in a solvent and then prepared into a solution as a coating material, or through mold casting, extrusion or injection molding. 10. The application according to claim 9, characterized in that the solvent is one selected from tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide and methyl ethyl ketone.

Images