CN1706887A - Composite carbon nanotube-polymer material for blood environment and its prepn process and application - Google Patents
Composite carbon nanotube-polymer material for blood environment and its prepn process and application Download PDFInfo
- Publication number
- CN1706887A CN1706887A CN 200410047906 CN200410047906A CN1706887A CN 1706887 A CN1706887 A CN 1706887A CN 200410047906 CN200410047906 CN 200410047906 CN 200410047906 A CN200410047906 A CN 200410047906A CN 1706887 A CN1706887 A CN 1706887A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- high molecular
- polymer
- solvent
- molecular polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The composite material for blood environment includes carbon nanotube and polymer and is prepared through dispersing carbon nanotube inside polymer through co-precipitation and controlling carbon nanotube adding amount in 1-6 wt%. Specifically, the preparation process includes dissolving hydrophilic carbon nanotube inside solvent, mixing with polymer solution, and adding initiator for co-precipitation. The composite carbon nanotube-polymer material has homogeneously dispersed carbon nanotube, may be re-dissolved in organic solvent, and is used as coating material on the surface of medical equipment or implanted false body in blood environment and as material for making artificial tissue, organ or intervented device.
Description
Technical field
The present invention relates to a kind of carbon nanotube-polymer composite that is used for biomedical sector, also relate to and its production and application.
Background technology
Carbon nanotube is the tubular carbon material that a class has perfect graphite-structure, and diameter is generally from several nanometers to tens nanometer.Carbon nanotube has good electroconductibility, electromagnetic property and excellent mechanical property, also has excellent biological compatibility simultaneously, and its comprehensive excellent properties has caused very big research interest at biomedical sector.
But because carbon nanotube has huge specific surface area, have very strong agglomeration each other, carbon nanotube is difficult to disperse in water and organic solvent, macromolecule matrix.About the research of carbon nanotube and organic macromolecule-based volume recombination, related polymkeric substance comprises Resins, epoxy, nylon, polyacrylic ester, urethane etc.In the preparation of these matrix materials, how even carbon nanotube being distributed in the polymeric matrix is key problem in technology, existing dispersing method mainly comprises: (1) is distributed to carbon nanotube in the polymers soln by effects such as ultrasonic resonance or powerful mechanical stirring, the problem that exists is that the method for sonic oscillation or mechanical powerful blend still is difficult to make carbon nanotube to evenly spread in the polymers soln fully, and the solution system poor stability that forms, general carbon nanotube add-on just reaches capacity when being 1-2%, carbon nanotube forms gathering and can't disperse (as document Phys Chem B 2002,106,2210).(2) at some organic molecule of carbon nano tube surface grafting or polymer, (as document Ya-ping Sun, et al., Functionalized Carbon Nanotubes:Properties and Applications.Acc.Chem.Res.2002,35,1096-1104), the grafted polymer is PPEI, PVK-PS, PS1, PEG, PVA-VA etc. increase the dispersiveness of carbon nanotube in solvent medium; These class methods have been introduced other material in system; (3) by adding tensio-active agent or coupling agent carbon nanotube is distributed in the monomer solution, initiated polymerization process then, form the carbon nano tube-polymer matrix material, (as document Harry J.et al., SWNT-filled Thermal plastic and Elastic compositeprepared by miniemulsion polymerization.Nanoletters 2 (8), 2002); Still there is the problem of method (1) to a certain extent in the matrix material that forms so as can be seen, and has introduced other materials such as tensio-active agent, initiator, needs the polymerization process through more complicated simultaneously.
The applied research of carbon nanotube in biomedical sector is up to the present still less relatively, and the main applied research of carbon nanotube relates to following aspect, comprises that (1) is used for bio-imaging with carbon nanotube as probe; (2), stop protein molecule at its surperficial non-specific binding and identification specific protein molecule by the finishing and the functionalization of carbon nanotube; (3) after modifying, biomolecules is used for the growth in vitro of neurocyte; And the Study on biocompatibility of (4) carbon nanotube.
When the carbon nanotube polymer composite being applied to specific biosystem (as the implant of cardiovascular systems, artificial organs, intervention conduit, blood circulation pipeline etc.), except the dispersiveness and stability that will guarantee carbon nanotube polymer composite system, also the special requirement material will keep the pure of its chemical constitution as far as possible, does not introduce other as far as possible to the uncertain component of biosystem effect in material; Also to improve the add-on of carbon nanotube in the macromolecule matrix and add-on that can controlling carbon nanotube in addition.At present, existing complex method with and product all can not satisfy this requirement.On the other hand, biomaterial need film forming form be applied to medicine equipment or the finishing of the property implanted prosthese to apply under many circumstances, perhaps adopt the mode of solution-cast moulding to make the built-in type device of various complicated shapes, this carbon nanotube-polymer composite that just need obtain can be mixed with certain density solution, uses under solution state; And the combination product of existing method development can not satisfy this requirement basically.
Summary of the invention
The purpose of this invention is to provide the carbon nanotube-polymer composite that is used for the blood contact environment.
Carbon nanotube-the polymer composite that is used for blood environment provided by the invention, comprise carbon nanotube and high molecular polymer, it is characterized in that, described carbon nanotube is dispersed in the described high molecular polymer through liquid phase coprecipitation, and definite controlling carbon nanotube add-on is at 1-6 weight %, wherein, described high molecular polymer is to be selected from a kind of in urethane, polyvinyl chloride, polyester, poly(lactic acid) and the lactic acid-ethanol copolymer.
Another object of the present invention is to provide the above-mentioned carbon nanotube of a kind of preparation-polymer composite method.
The preparation method of this carbon nanotube-polymer composite provided by the invention comprises the steps:
1) carbon nanotube is carried out surface treatment, form hydroxy-acid group, obtain hydrophilic carbon nano tube in carbon nano tube surface;
2) select the different solvent composition cosolvent of two or more polarity, the water miscible even carbon nanotube that step 1) is obtained is dispersed in the cosolvent;
3) high molecular polymer being dissolved in the organic solvent, step 2) solution of carbon nanotube-cosolvent of obtaining and the solution of high molecular polymer-organic solvent mixes, and forms carbon nanotube-high molecular polymer-solvent system;
4) in carbon nanotube-high molecular polymer-solvent system, add the triggering agent, carbon nanotube and high molecular polymer coprecipitation are come out, obtain throw out;
5) substitution method is removed in the step 4) not volatile solvent in the throw out, obtains carbon nanotube-polymer composite.
In the aforesaid method, the described carbon nanotube of step 1) carries out surface treatment and is meant with mixing acid carbon nanotube was carried out supersound process 10-120 minute in the 10-80KHz frequency, and described mixing acid can be two or more the mixing in hydrochloric acid, nitric acid, sulfuric acid, acetate, butyric acid, the toxilic acid.
Step 2) described cosolvent is two or more the mixing that is selected from water, tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, butanols, acetone, butanone, ritalin, the vinyl acetic monomer, wherein preferably water, methyl alcohol, ethanol, tetrahydrofuran (THF).
The described triggering agent of step 4) is water, methyl alcohol, ethanol, butanols, acetone or butanone, preferably water, methyl alcohol, ethanol, and temperature is 0-60 ℃ during co-precipitation.
Boiling point is low in order to select for the described substitution method of step 5), high volatility, with step 3) in organic solvent dissolve each other with the insoluble solvent exchange matrix material of polymkeric substance in not volatile organic solvent.
A further object of the present invention provide above-mentioned carbon nanotube-polymer composite with the direct contact environment of blood in application.
This application medicine equipment that at first to be above-mentioned carbon nanotube-polymer composite use in blood environment as coated material or the application of the property implanted prosthetic surface, or as the application of starting material on manufacture of intraocular tissue, organ or intervention property device.In the application, need carbon nanotube-polymer composite is dissolved in and be mixed with behind the solvent behind the solution as coated material, or by die casting, extrude or injection molding; Described solvent is to be selected from a kind of in tetrahydrofuran (THF), dioxane, dimethyl formamide, N,N-DIMETHYLACETAMIDE, the methyl ethyl ketone.
The present invention proposes a kind of preparation method of new carbon nanotube-polymer composite, make carbon nanotube and macromolecular material in a kind of cosolvent system, form mixture, even carbon nanotube is dispersed in the compound system, the carbon nanotube add-on can change at 1-6% (weight percent) in the mixture, and the definite add-on of controlling carbon nanotube; This mixture can be mixed with solution as required, casting film or coating, also directly extrusion moulding or extrude as masterbatch and other material blend on base material.
Description of drawings
The carbon nanotube Electronic Speculum figure of Fig. 1 for using among the present invention.
Fig. 2 A is carbon nanotube-urethane in the preparation process of the present invention-cosolvent system stability experiment figure.
Fig. 2 B is carbon nano-tube aqueous solutions-urethane in the control experiment-tetrahydrofuran solution system stability experiment figure.
Fig. 3-A is the stereoscan photograph of the section of the carbon nanotube-compound polyurethane material of the present invention's preparation.
Fig. 3-B is the DSC spectrum of the carbon nanotube-compound polyurethane material of the present invention's preparation.
Fig. 4-A is the carbon nanotube-compound polyurethane material of the present invention's preparation.
Fig. 4-B is 5% tetrahydrofuran solution of the carbon nanotube-compound polyurethane material of the present invention's preparation and the form photo of contrast sample solution, wherein, 1# is a matrix material tetrahydrofuran solution of the present invention, 2# is carbon nanotube solution behind the ultra-sonic dispersion in the urethane tetrahydrofuran solution, and 3# is a polyurethane solution.
Fig. 4-C is the optical microscope photograph (25 * 16) of Fig. 4-B solution correspondence.
Fig. 5 is the IABP balloon catheter of making of the carbon nanotube of the present invention's preparation-compound polyurethane material.
Fig. 6-A is thrombocyte (human blood) the Electronic Speculum figure that is adsorbed on polyurethane surface.
Fig. 6-B is thrombocyte (human blood) the Electronic Speculum figure that is adsorbed on the carbon nanotube-compound polyurethane material surface of the present invention's preparation.
Fig. 7-A is thrombocyte (sheep blood) the Electronic Speculum figure that is adsorbed on polyurethane surface;
Fig. 7-B is thrombocyte (sheep blood) the Electronic Speculum figure that is adsorbed on the carbon nanotube-compound polyurethane material surface of the present invention's preparation.
Fig. 8 is the contact material surface positive rate of platelet membrane surface GPIIb/IIIa in the platelet rich plasma after 15 minutes.
Fig. 9 is the hemolysis rate of the carbon nanotube-compound polyurethane material of the present invention's preparation.
Pellet and other forming composition that Figure 10 makes for the carbon nanotube-compound polyurethane material of the present invention's preparation.
Embodiment
Below from several respects in detail the present invention is described in detail.
The present invention at first provides a kind of method for preparing carbon nanotube-polymer composite in cosolvent system.Characteristics of the present invention are that (1) does not introduce organic molecule or polymer in carbon nano tube surface, and the carbon nanotube after the surface treatment only has oxy radicals such as carboxyl, hydroxyl, ether oxygen base; (2) do not need to begin to carry out macromolecular polymerization reaction, can be directly the cosolvent solution of carbon nanotube be mixed with multiple macromolecular solution, obtain the finely dispersed composite prod of carbon nanotube from monomer; (3) the carbon nanotube add-on can change at 1-6% (weight percent) in the matrix material, and the definite add-on of controlling carbon nanotube; (4) matrix material can be mixed with solution as required, casting film or coating, also directly extrusion moulding or extrude as masterbatch and other material blend on base material.
Method of the present invention is, after carbon nanotube carried out water-soluble processing, evenly spread in the cosolvent of the different solvent composition of two or more polarity, and then mix with the high molecular polymer that is dissolved in the organic solvent, forming stable common solution is, produces carbon nanotube-polymer composite that co-precipitation obtains excellent dispersion by triggering the agent effect.This method guarantees that by the cosolvent of selecting to be fit to carbon nanotube can homodisperse in solvent, thereby obtains product by liquid phase coprecipitation, has guaranteed that carbon nanotube can homodisperse in high molecular polymer in the composite prod.The dispersiveness of carbon nanotube in compound system be one of for matrix material characteristics of the present invention, and the characteristics that the present invention should dispersiveness have specifically been verified in experiment two.
In the present invention, used carbon nanotube is a multi-walled carbon nano-tubes, caliber is 30-50nm, length＞2 μ m, referring to Fig. 1, can can be in urethane, polyvinyl chloride, polycarbonate, Resins, epoxy, polyester, poly(lactic acid), polyglycolic acid, the lactic acid-ethanol copolymer any, optimization polyurethane with carbon nanotube compound high molecular polymer.
In the methods of the invention, carbon nanotube being carried out the surface-treated method can have: the sonic oscillation under proper temperature with carbon nanotube and certain proportion blended acid solution.In the embodiment of the invention, adopt the method for supersound process, with mixing acid carbon nanotube was carried out supersound process 10-120 minute with the 10-80KHz frequency, described mixing acid can be two or more the mixing in hydrochloric acid, nitric acid, sulfuric acid, acetate, butyric acid, the toxilic acid.
In the methods of the invention, the solvent that disperses to have water-soluble carbon nanometer tube can form cosolvent, wherein preferably water, methyl alcohol, ethanol, tetrahydrofuran (THF), dioxane for two or more the mixing in water, tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, butanols, acetone, butanone, ritalin, the vinyl acetic monomer.
In the inventive method, the triggering agent of co-precipitation is water, methyl alcohol, ethanol, butanols, acetone or butanone, preferably water, methyl alcohol, ethanol, and temperature is 0-60 ℃ during co-precipitation.
In the inventive method, have not volatile solvent in the coprecipitated product, in the aftertreatment, need these removal of solvents can be adopted substitution method.
The concrete preparation method of the present invention is referring to embodiment one to two.
Embodiment one, preparation carbon nanotube-compound polyurethane material
(1), take by weighing 0.25 gram carbon nanotube in round-bottomed flask, add 40 milliliters of the vitriol oil/concentrated nitric acids of 2: 1.Supersound process is 10 minutes under 25KHz; (2), be the membrane filtration of 100nm and wash to neutral drying with big water gaging dilution and with the aperture; (3), 90 milligrams of carbon nanotubes after will handling join in 60 milliliter 60% the methanol aqueous solution and disperse; (4), the dioxane solution of the urethane of preparation 5% is 60 milliliters; (5), (3) are slowly joined in (4), obtain uniform dark solution; (6), dropping 95% ethanol to co-precipitation takes place in (5), obtains uniform black precipitate; (7) throw out is cut into grain of rice size, and embathe product repeatedly with 95% ethanol, dry in vacuum drying oven under 50 ℃ afterwards, obtain carbon nanotube-compound polyurethane material.In this example, in whole compound system, the controlling carbon nanotube add-on is 3%.
Embodiment two, preparation carbon nanotube-polyvinyl chloride composite materials
Adopt the identical method of embodiment one, wherein, mixing acid is concentrated nitric acid and concentrated hydrochloric acid, cosolvent is tetrahydrofuran (THF), vinyl acetic monomer, water, high molecular polymer is a polyvinyl chloride, and triggering agent during co-precipitation is methyl alcohol, and resulting product is carbon nanotube-polyvinyl chloride composite materials.In this example, in whole compound system, the controlling carbon nanotube add-on is 1%.
Embodiment three, preparation carbon nanotube-compound polyurethane material, wherein the carbon nanotube add-on is 6%
Adopt the identical method of embodiment one, wherein, with polyurethane solution blended carbon nanotube be 180 milligrams.
According to the foregoing description, carry out following experiment:
Experiment one: the composite effect of differential scanning calorimetry method (DSC) analysis for carbon nanotubes-polymkeric substance
Under nitrogen atmosphere, with the speed intensification of 20 ℃/min, the thermal behavior of record carbon nanotube-compound polyurethane material (carbon nanotube add-on 3%) is a reference sample with urethane.The result is by shown in Fig. 3 B.Can see by the DSC spectrogram, with carbon nanotube compound after, original two endotherm(ic)peaks of polyurethane material are close mutually, illustrating has stronger interaction between carbon nanotube and the polyurethane molecular, formed good compound system.
Experiment two, the compound and degree of scatter of scanning electron microscopic observation carbon nanotube in polymkeric substance
Be that the pellet of carbon nanotube-compound polyurethane material of 3% was placed in the liquid nitrogen 30 minutes with the carbon nanotube add-on, break immediately after the taking-up, metal spraying on end face, observe cross-section morphology down in scanning electron microscope (S-5200), the result as shown in Figure 3A, as we can see from the figure, the carbon nanotube that significantly is not pulled out on the section, whole section is the characteristics of elastic breakdown.Illustrate formed between the carbon nano tube polyurethane matrix good compound.
Experiment three, the stability experiment of carbon nanotube in polymers soln
In embodiment one, get carbon nanotube-urethane in the step (5)-cosolvent sample, place beaker to make experiment sample (1); The carbon nano-tube aqueous solutions that other gets same concentration directly joins the sample sample (2) in contrast in the 5% urethane tetrahydrofuran solution, observe the solution changing conditions, urethane in is in the same old way separated out immediately, can not form uniform mixture with carbon nanotube, and the experiment sample can keep stable even dark solution, polymkeric substance do not occur and separate out and the carbon nanotube clustering phenomena, referring to Fig. 2 A and 2B.This description of test, carbon nanotube dispersiveness in urethane-cosolvent system is better, and system stability is good.
Experiment four, carbon nanotube-compound polyurethane material is mixed with 5% tetrahydrofuran solution after, the dispersiveness of carbon nanotube experiment in the solution:
In carbon nanotube-compound polyurethane material dissolving tetrahydrofuran (THF) with embodiment one preparation, be mixed with 5% solution, place (1) test tube, sampling simultaneously is applied on the slide glass, observes the dispersion situation of carbon nanotube under opticmicroscope; Other gets carbon nanotube after the surface treatment of same ratio and directly joins in 5% the urethane tetrahydrofuran solution, ultra-sonic dispersion is 30 minutes under 25KHz, place (2) test tube sample in contrast, get simultaneously be applied on the slide glass in the same old way, under opticmicroscope, observe the dispersion situation of carbon nanotube.The microscopically result shown in Fig. 4 C, can see the dispersion situation of carbon nanotube in solution in the 1# test tube significantly better than in the 2# test tube in the same old way; From leaving standstill the observation of test tube, referring to Fig. 4 B, (1) test tube-directly keep solution state, layering does not appear, and demixing phenomenon appears in (2) test tube solution very soon, illustrate that matrix material of the present invention not only can be mixed with solution again and use, and carbon nanotube still can maintain stability dispersed preferably and maintenance solution in the solution of preparation.
The present invention with the method for experiment one to four, has verified the matrix material that embodiment two and three obtains simultaneously, has also obtained identical result, does not exemplify one by one at this.According to above-mentioned experiment, determined to use method of the present invention, when the add-on of carbon nanotube reaches 6%, the stability of solution in the time of still can guaranteeing the stability of system in the preparation process and be mixed with solution again when matrix material used.
The present invention continues to provide the application of carbon nanotube-polymer composite in the blood contact environment of method for preparing.
As noted earlier, when the carbon nanotube polymer composite is applied in the blood contact environment (as the implant of cardiovascular systems, artificial organs, intervention conduit, blood circulation pipeline etc.), except the dispersiveness and stability that will guarantee carbon nanotube polymer composite system, also the special requirement material will keep the pure of its chemical constitution as far as possible, does not introduce other as far as possible to the uncertain component of biosystem effect in material.Carbon nanotube polymer composite provided by the invention does not contain other stablizer, table agent alive and grafted polymer or organic compound in the system, can meet this requirement well.Below with the application of specific embodiment explanation carbon nanotube polymer composite of the present invention, these embodiment can not be interpreted as the restriction to this matrix material Application Areas.
Example one: matrix material is as the application of anticoagulant coatings in the blood contact environment
With matrix material of the present invention, be mixed with 5% solution with tetrahydrofuran (THF), make test tube with applying film forming method; Use same quadrat method, make test tube sample in contrast with urethane.Extract Healthy Sheep venous blood, prepare platelet rich plasma (PRP) according to standard method.PRP joined to hatch in the sample hose after 1 hour take out, with the not adherent thrombocyte of PBS (pH=7.4) damping fluid flush away, with standard method fix, dewater, behind dry, the metal spraying, under scanning electron microscope, observe platelet adhesion reaction quantity and form, referring to Fig. 7 A, Fig. 7 B, the result shows: platelet adhesion reaction quantity that carbon nanotube-compound polyurethane material (Fig. 7 A) surface causes and activation degree all significantly are lower than (Fig. 7 B) in the same old way.
Example two: with same test tube, gather healthy support person's venous blood, prepare platelet suspension and blood plasma according to standard program; Adsorb at specimen surface with blood plasma earlier, form the plasma proteins adsorption layer, again platelet suspension is joined in the test tube, hatch after 1 hour and take out, with the not adherent thrombocyte of PBS (pH=7.4) damping fluid flush away, with standard method fix, dewater, behind dry, the metal spraying, under scanning electron microscope, observe platelet adhesion reaction quantity and form, referring to Fig. 6 A, Fig. 6 B, the result shows: platelet adhesion reaction quantity that carbon nanotube-compound polyurethane material (Fig. 6 A) surface causes and activation degree all significantly are lower than (Fig. 6 B) in the same old way.
Example three: with same test tube, gather healthy volunteer's venous blood, prepare platelet rich plasma (PRP) according to standard program.PRP joined to hatch in the sample hose after 15 minutes take out, with PAC-1 mark activatory thrombocyte, with hematoblastic activation rate among the flow cytometry PRP, the result is referring to Fig. 8, and hematoblastic activation rate significantly reduces among the PRP that demonstration carbon nanotube-compound polyurethane material causes.
Example four: with same test tube, gather healthy support person's venous blood, to join in the test tube to be measured after 0.2 milliliter of blood and the mixing of 10 ml physiological salines, hatched under 37 ℃ 1 hour, under 2000rpm centrifugal 10 minutes, get supernatant liquor and under 540nm, measure the concentration of oxyphorase in the solution, calculate the haemolysis degree according to formula.The result shows that referring to Fig. 9 the haemolysis degree that carbon nanotube-compound polyurethane material causes significantly reduces.
Example five: make intervention property conduit
Carbon nanotube-compound polyurethane material is mixed with 5% tetrahydrofuran solution, carbon nano-tube coating-compound polyurethane material outside polyurethane catheter, make air bag with applying film-forming process simultaneously, the anti-effect of fighting of air bag meets the experimentation on animals requirement, and the air bag product of making is referring to Fig. 5.
Example six: make pellet and various molding materials
Carbon nanotube-the polymer composite of the present invention's preparation is a kind of black precipitate, after washing, oven dry, can directly be made into pellet; Also can be dissolved in the solvent, inject mould, make different shape as required.Referring to Figure 10, pellet is wherein arranged, circle and square material behind mould molding are also arranged.These materials can be further used as the preparation medicine equipment, as the raw material of artificial organ, organ or intervention property device.
Claims (10)
1, a kind of carbon nanotube-polymer composite that is used for blood environment, comprise carbon nanotube and high molecular polymer, it is characterized in that, described carbon nanotube is dispersed in the described high molecular polymer through liquid phase coprecipitation, and definite controlling carbon nanotube add-on is at 1-6 weight %, wherein, described high molecular polymer is to be selected from a kind of in urethane, polyvinyl chloride, polyester, poly(lactic acid) and the lactic acid-ethanol copolymer.
2, carbon nanotube-polymer composite according to claim 1 is characterized in that, described liquid phase coprecipitation comprises the steps:
1) carbon nanotube is carried out surface treatment, form hydroxy-acid group, obtain hydrophilic carbon nano tube in carbon nano tube surface;
2) select the different solvent composition cosolvent of two or more polarity, the water miscible even carbon nanotube that step 1) is obtained is dispersed in the cosolvent;
3) high molecular polymer being dissolved in the organic solvent, step 2) solution of carbon nanotube-cosolvent of obtaining and the solution of high molecular polymer-organic solvent mixes, and forms carbon nanotube-high molecular polymer-solvent system;
4) in carbon nanotube-high molecular polymer-solvent system, add the triggering agent, carbon nanotube and high molecular polymer coprecipitation are come out, obtain throw out;
5) substitution method is removed in the step 4) not volatile solvent in the throw out, obtains carbon nanotube-polymer composite.
3, a kind of preparation method of carbon nanotube-polymer composite is characterized in that, comprises the steps:
1) carbon nanotube is carried out surface treatment, form hydroxy-acid group, obtain hydrophilic carbon nano tube in carbon nano tube surface;
2) select the different solvent composition cosolvent of two or more polarity, the hydrophilic even carbon nanotube that step 1) is obtained is dispersed in the cosolvent;
3) high molecular polymer being dissolved in the organic solvent, step 2) solution of carbon nanotube-cosolvent of obtaining and the solution of high molecular polymer-organic solvent mixes, and forms carbon nanotube-high molecular polymer-solvent system;
4) in carbon nanotube-high molecular polymer-solvent system, add the triggering agent, carbon nanotube and high molecular polymer coprecipitation are come out, obtain throw out;
5) substitution method is removed in the step 4) not volatile solvent in the throw out, obtains carbon nanotube-polymer composite.
4, according to the preparation method of the described carbon nanotube-polymer composite of claim 3, it is characterized in that, the described carbon nanotube of step 1) carries out surface treatment and is meant with mixing acid carbon nanotube was carried out supersound process 10-120 minute in the 10-80KHz frequency, and described mixing acid can be two or more the mixing in hydrochloric acid, nitric acid, sulfuric acid, acetate, butyric acid, the toxilic acid
5, according to the preparation method of the described carbon nanotube-polymer composite of claim 3, it is characterized in that, step 2) described cosolvent is two or more the mixing that is selected from water, tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, butanols, acetone, butanone, ritalin, the vinyl acetic monomer, wherein preferably water, methyl alcohol, ethanol, tetrahydrofuran (THF).
According to the preparation method of the described carbon nanotube-polymer composite of claim 3, it is characterized in that 6, the described triggering agent of step 4) is water, methyl alcohol, ethanol, butanols, acetone or butanone, preferably water, methyl alcohol, ethanol, temperature is 0-60 ℃ during co-precipitation.
7, according to the preparation method of the described carbon nanotube-polymer composite of claim 3, it is characterized in that, boiling point is low in order to select for the described substitution method of step 5), high volatility, with step 3) in organic solvent dissolve each other, with the insoluble solvent exchange matrix material of polymkeric substance in not volatile organic solvent.
8, the medicine equipment that in blood environment, uses as coated material of carbon nanotube-polymer composite or the application of the property implanted prosthetic surface, or as the application of starting material on manufacture of intraocular tissue, organ or intervention property device.
9, application according to claim 8 is characterized in that, described carbon nanotube-polymer composite is dissolved in and is mixed with behind the solvent behind the solution as coated material, or by die casting, extrude or injection molding.
10, application according to claim 9 is characterized in that, described solvent is to be selected from a kind of in tetrahydrofuran (THF), dioxane, dimethyl formamide, N,N-DIMETHYLACETAMIDE, the methyl ethyl ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410047906 CN1706887B (en) | 2004-06-10 | 2004-06-10 | Composite carbon nanotube-polymer material for blood environment and its preparation process and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410047906 CN1706887B (en) | 2004-06-10 | 2004-06-10 | Composite carbon nanotube-polymer material for blood environment and its preparation process and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1706887A true CN1706887A (en) | 2005-12-14 |
| CN1706887B CN1706887B (en) | 2010-04-28 |
Family
ID=35581008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410047906 Expired - Fee Related CN1706887B (en) | 2004-06-10 | 2004-06-10 | Composite carbon nanotube-polymer material for blood environment and its preparation process and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1706887B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235193B (en) * | 2008-01-15 | 2010-12-08 | 北京科技大学 | Method for preparing degradable biocompatibility macromolecule/carbon nano-tube composite material |
| CN102813969A (en) * | 2012-07-27 | 2012-12-12 | 上海交通大学医学院附属新华医院 | Degradable nano composite hollow viscera bracket having strengthening and toughening effects |
| CN113244458A (en) * | 2021-05-08 | 2021-08-13 | 康膝生物医疗(深圳)有限公司 | Composite material for repairing articular cartilage damage and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176142C (en) * | 2002-03-14 | 2004-11-17 | 四川大学 | Polymer/carbon nano pipe composite powder and its solid phase shear break up preparation method |
| US6936653B2 (en) * | 2002-03-14 | 2005-08-30 | Carbon Nanotechnologies, Inc. | Composite materials comprising polar polymers and single-wall carbon nanotubes |
| CN1207186C (en) * | 2003-07-31 | 2005-06-22 | 上海交通大学 | Super-branched polymer grafted carbon nanotube and its prepn process |
-
2004
- 2004-06-10 CN CN 200410047906 patent/CN1706887B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235193B (en) * | 2008-01-15 | 2010-12-08 | 北京科技大学 | Method for preparing degradable biocompatibility macromolecule/carbon nano-tube composite material |
| CN102813969A (en) * | 2012-07-27 | 2012-12-12 | 上海交通大学医学院附属新华医院 | Degradable nano composite hollow viscera bracket having strengthening and toughening effects |
| CN113244458A (en) * | 2021-05-08 | 2021-08-13 | 康膝生物医疗(深圳)有限公司 | Composite material for repairing articular cartilage damage and preparation method thereof |
| CN113244458B (en) * | 2021-05-08 | 2022-07-08 | 康膝生物医疗(深圳)有限公司 | Composite material for repairing articular cartilage damage and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1706887B (en) | 2010-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dodero et al. | Multilayer alginate–polycaprolactone electrospun membranes as skin wound patches with drug delivery abilities | |
| Wongkanya et al. | Electrospinning of alginate/soy protein isolated nanofibers and their release characteristics for biomedical applications | |
| Unal et al. | Glioblastoma cell adhesion properties through bacterial cellulose nanocrystals in polycaprolactone/gelatin electrospun nanofibers | |
| Zhao et al. | In situ cross-linking of stimuli-responsive hemicellulose microgels during spray drying | |
| Chuysinuan et al. | Enhanced structural stability and controlled drug release of hydrophilic antibiotic-loaded alginate/soy protein isolate core-sheath fibers for tissue engineering applications | |
| CN1944529A (en) | Process for preparing biologically degradable SiO2/poly lactic acid nano composite material | |
| CN111012947B (en) | Injectable and self-healing starch-based hydrogel and preparation method and application thereof | |
| Liu et al. | Ultrasound-mediated preparation and evaluation of a collagen/PVP-PCL micro-and nanofiber scaffold electrospun from chloroform/ethanol mixture | |
| Zhang et al. | Fabrication of a high-toughness polyurethane/fibroin composite without interfacial treatment and its toughening mechanism | |
| Hu et al. | Slow-release lubrication of artificial joints using self-healing polyvinyl alcohol/polyethylene glycol/graphene oxide hydrogel | |
| Feng et al. | Polydopamine constructed interfacial molecular bridge in nano-hydroxylapatite/polycaprolactone composite scaffold | |
| CN111424425A (en) | Nano hemostatic and antibacterial composite material for vascular surgery and preparation method thereof | |
| CN1706887B (en) | Composite carbon nanotube-polymer material for blood environment and its preparation process and application | |
| Al-Madhagy et al. | Evaluation of the chemical, morphological, physical, mechanical, and biological properties of chitosan/polyvinyl alcohol nanofibrous scaffolds for potential use in oral tissue engineering | |
| Foroughi et al. | Hydrogels Fibers | |
| Huang | Tuning gelatin–alginate bioink properties by introducing new decellularized elastic cartilage scaffolds for bioinspired composite membranes in orthopedics | |
| El-Aassar et al. | Chemical crosslinking of poly (vinyl alcohol)/poly ethylene glycol with glutaraldehyde nanofibers | |
| CN102875733B (en) | Nanoparticles with epicyte-imitated structure and preparation method thereof | |
| JP6963638B2 (en) | Polymer object with functionalized surface and its manufacturing method | |
| KR101816297B1 (en) | Modified nanofibril, method for the preparation thereof and use thereof | |
| Zulkifli et al. | Polycaprolactone/Chlorophyllin Sodium Copper Salt Nanofibrous Mats Prepared by Electrospinning for Soft Tissue Engineering | |
| CN111150879A (en) | Thrombus-promoting and X-ray developing suppository and preparation method and application thereof | |
| CN1908034A (en) | Crosslinking poly(organophosphazenes) micron tube and preparation method thereof | |
| Nabat et al. | Effect of PEG on Structure and Physical Properties of PVA/CMC Nanofiber | |
| Neira-Carrillo et al. | Templated CaCO3 crystallization by submicrometer and nanosized fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100428 |