CN101235193B - Method for preparing degradable biocompatibility macromolecule/carbon nano-tube composite material - Google Patents
Method for preparing degradable biocompatibility macromolecule/carbon nano-tube composite material Download PDFInfo
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Abstract
The invention provides a preparation process of degradable biocompatible macromolecule/ carbon nano pipe composite material, relating to the preparation of biocompatible degradable macromolecule/ carbon nano pipe composite material which has high strength and high toughness. The invention adopts the technique of conducting surface activating, multiple phase solution dispersion, casing formation and heating processing for the carbon nano pipe with carboxylation and surface activator to prepare biological medical degradable polymer or carbon nano pipe composite material, which reduces the aggregation and entanglement phenomenon of the carbon nano pipe in solution, solves the problem of aggregating of the carbon nano pipe in macromolecules, forms firm interface interacting action with the polymer, thereby obviously increasing the mechanical property of degradable macromolecule. The carbon nano pipe/degradable macromolecule composite material with different dimension and shape which has high strength and high toughness can be obtained, in particular to reinforced polymer composite material of acidulating carbon nano pipe, wherein the tension strength is increased over 6.50 MPa, elasticity modulus is increased over 250 MPa, which has excellent surface wettability, adsorbability to protein and biomolecule, cellular affinity and biological degradation.
Description
Technical field
The present invention relates to biomedical materials field, particularly the preparation of high-intensity high-tenacity biocompatibility degradable macromolecule/carbon nano tube compound material.
Background technology
Carbon nanotube is the airtight nanometer body that is bent to form by single or multiple lift six-membered carbon ring graphite linings, and the two ends of pipe respectively are the hemispherical end-blocking of similar half fullerene molecule, and length-to-diameter ratio is generally greater than 1000.The unique texture of this novel accurate one dimension functional materials makes it have excellent mechanics, electricity and thermal property.Perfect vertically C-C and the enclosed construction of arranging of carbon nanotube, cause its axial strength and Young's modulus high, be about 100～600GPa as the carbon nanotube tensile strength, than high two orders of magnitude of existing high-strength carbon fiber, higher more than 100 times than the intensity of steel, theoretical Young's modulus can be up to 1.8 * 10
12Pa, and proportion is the 1/6-1/7 of steel, is to have the highest material of specific tenacity at present.In addition, carbon nanotube is acidproof, alkaline-resisting, high temperature resistant, has high chemistry and thermostability.In recent years, the carbon nanotubes reinforced polymer matrix material has been carried out big quantity research both at home and abroad, confirmed carbon nanotube, can improve mechanical property and other physicals of polymkeric substance greatly as wild phase and conductive phase.The polymkeric substance that relates to comprises polystyrene, polyethylene, polymethylmethacrylate, polymeric amide, polyaniline, tens of kinds of polymkeric substance such as polyvinyl alcohol.
Carbon material has excellent biological compatibility, and excellent anticoagulant property and blood compatibility do not influence the protein in the blood plasma and the activity of enzyme; In human body, do not react and dissolve, corrode and other untoward reaction; Good lubricity and fatigue resistance are arranged in addition, and the mechanics matching of human body soft tissue and sclerous tissues, thereby in hard tissue repair, be used widely in cardiovascular material aspect.
Polyglycolic acid (PGA), poly(lactic acid) (PLA), poly (hydroxyalkanoate) (PHA), poly-own interior acid esters (PCL), degradable synthesized polymers such as poly-acid anhydrides, because of having excellent biological compatibility, and degraded product is nontoxic, have been widely used in the bio-medical field, as surgical sutures, adsorbable bone immobilization material, medicament slow release material, tissue engineering bracket material etc.But it is not enough that these materials exist in directions such as mechanical property, wetting ability and cellular affinities, and the modification of these materials being carried out physics and chemistry is the focus in medical polymer field always.
Utilize the biocompatibility of carbon nanotube, excellent mechanical property and physiological stability, carry out compound with above-mentioned degradable biological polymer, preparation high-intensity high-tenacity biocompatibility degradable polymer/carbon nano tube compound material, can be when keeping biopolymer good biocompatibility and degradation property, improve its mechanical property and condition of surface greatly, the bio-medical material of obtained performance excellence, can be widely used in various soft/the hard tissue regeneration reparation, and organizational project organ culture etc.
Because big specific surface area of carbon nanotube and strong interaction and cluster that very easily spontaneous formation diameter is 10～100nm, when the preparation carbon nano-tube/polymer composite material, its interfacial property makes his nanotube be difficult to homodisperse in polymeric system, and exist with larger-size aggregating state, influenced reinforced effects and the function of carbon nanotube in polymeric matrix, and the moulding processability of polymer/carbon nano-tube matrix material.Existing chemical modification and purification process technology all fail effectively to solve this difficult problem.At above-mentioned present situation, the present invention adopts carbon nano tube surface activation, the dispersion of complex phase solution, casting and heat-treatment technology method to prepare biological medical degradable polymer/carbon nano-tube matrix material.Wherein adopt kinds of surface promoting agent and strong acid that carbon nanotube is carried out surface active, introduce hydrophilic or hydrophobic functional group in carbon nano tube surface, to strengthen the interfacial interaction of carbon nanotube and degradable polymer, help the stress transmission between the matrix material two-phase.The complex phase solution dispersion method of employing under ultrasonication, by selecting and the massfraction ratio of control solvent species, ultrasonic intensity and action time, carbon nanotube and polymkeric substance, temperature of reaction etc., break between the carbon nanotube aggregating state that forms owing to big specific surface area and strong interaction, improve its dispersiveness in solution and in polymeric matrix.Conditions such as the temperature by control casting and aftertreatment, pressure in addition, obtain different aggregated structures and surface topography, with this obtain mechanical property, surface wettability, to protein and biomolecules adsorptivity and cellular affinity and the regulatable medical bio macromolecule/carbon nano-tube composite material of biological degradability.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of biocompatibility medical bio macromolecule/carbon nano-tube composite material, make biocompatibility degradable macromolecule/carbon nano tube compound material of preparing have excellent mechanical property, surface wettability, to protein and biomolecules adsorptivity and cellular affinity and biological degradability, and can regulate and control above-mentioned performance according to service requirements.
The present invention adopts surface active, the dispersion of complex phase solution, casting and heat-treatment technology method to prepare the medical bio macromolecule/carbon nano-tube composite material.Processing step is as follows:
Step 1: the surface active of carbon nanotube
Method 1: carbon nanotube is added in the strong acid solution with 1-15g/L, under the 70-140 ℃ of condition, stirring and refluxing 3-12 hour, continue backflow 1-4 hour under the room temperature; With adding deionized water and centrifugation in this strong acid solution, remove the acid that remains in the solution, be neutral substantially until solution; With dry 12-24 hour of solution, fully remove residual water-content then; The carbon nanotube that obtains is ground 10-60min, obtain carboxylic carbon nano-tube; Described carbon nanotube is a Single Walled Carbon Nanotube, external diameter scope≤2nm, length 1-15 μ m, perhaps multi-walled carbon nano-tubes, external diameter scope 5-100nm, length 1-15 μ m.Strong acid is the vitriol oil, or concentrated nitric acid, or the mixing acid of the sulfuric acid of 1/100-100/1 volume ratio and nitric acid, or the mixing acid of the hydrochloric acid of 1/100-100/1 volume ratio and nitric acid.
Method 2: under the room temperature, analytical pure tensio-active agent etc. is joined solution for 0.001-5g/mL, be stirred to dissolving fully at 20-80 ℃ of heating in water bath; In this surfactant soln, add carbon nanotube; With ultra-sonic dispersion instrument batch process 1-60min, hyperacoustic power is 50-450W.The weight percent of tensio-active agent and carbon nanotube is 0.5%-10%.With the mixed solution centrifugation, remove water layer, and place vacuum drying oven.Thorough drying is ground to constant weight, obtains the surface active carbon nanotube.Described tensio-active agent is a kind of in polyvinylpyrrolidone, benzene sulfonic acid sodium salt, sodium sulfonate, calcium sulphonate, ammonium sulphonate, sodium sulfate, the trimethyl-glycine.
Step 2: the dispersion of carbon nano-tube/polymer complex phase solution
Polymkeric substance is added in the following organic solvent, and concentration is 1-100mg/ml, is back to dissolving fully in 50-90 ℃ water-bath.Carboxylic carbon nano-tube or surface active carbon nanotube that adding is obtained by step 1, the carbon nanotube mass percent that adds is 0.01%-20%, ultra-sonic dispersion 2-60min, the power of ultra-sonic dispersion is 50-450W, obtains uniform carbon nano-tube/polymer complex phase solution.Described polymkeric substance is polyglycolic acid (PGA), poly(lactic acid) (PLA), PHA (PHA), poly-a kind of in acid esters (PCL), poly-acid anhydrides, polyamino acid, the polyphosphonitrile in oneself, and described organic solvent is a kind of in methylene dichloride, chloroform, tetrahydrofuran (THF), dimethylbenzene, the acetone.
Step 3: casting and thermal treatment
Used mould in preheated mold, leaves standstill 1-5min with the complex phase solution casting of step 2 gained after preheating under 30-100 ℃ the temperature, get rid of the bubble in the solution.Under-5-90 ℃ condition, evaporate a large amount of solvents, drying and moulding at room temperature then, perhaps direct drying and moulding under normal temperature condition.The thickness 5-300 μ m of the film that obtains after the moulding.
Compared with prior art, the present invention adopts carboxylated and tensio-active agent carries out surface active to carbon nanotube, carbon nanotube impurity after the activation reduces, and in conjunction with carboxyl and surfactant group, has reduced gathering and the entanglement phenomenon of carbon nanotube in solution on the carbon nano tube surface.Can homodisperse in biological macromolecular solution, solved the agglomeration traits of carbon nanotube in polymer, and with the firm interfacial interaction of polymer formation, obviously improve the mechanical property of degradable macromolecule.Adopt the dispersion of complex phase solution, casting and heat-treatment technology method to prepare biomedical polymer/carbon nano tube compound material in addition, its surface topography of may command and aggregated structure, by changing the temperature and the post-treatment condition of moulding process, can obtain the carbon nanotube/degraded macromolecular matrix material of the high strength and the high tenacity of different size and shape.Especially acidifying carbon nanotube enhanced polymer composites, tensile strength is brought up to more than the 6.50MPa by 3.88MPa, and Young's modulus is brought up to (as Fig. 1, shown in Figure 2) more than the 250MPa by 145MPa.In addition this material surface wettability, to protein and biomolecules adsorptivity and cellular affinity and the good (see figure 3) of biological degradability.Toughness reinforcing biocompatibility degradable macromolecule/the carbon nano tube compound material technological process is simple, easy to operate should to invent the enhancing for preparing in addition, good reproducibility.
Description of drawings
Curve 1 is the stress-strain(ed) curve of polyhydroxybutyrate valerate among Fig. 1, and curve 2 is stress-strain(ed) curves that the acidifying carbon nanotube strengthens polyhydroxybutyrate valerate matrix material;
Fig. 2 is the Young's modulus of compound front and back material;
Fig. 3 is the growing state of cell on composite material film.
Embodiment
Example one:
Carbon nanotube (multi-walled carbon nano-tubes, internal diameter 80-100nm, length 1-2 μ m) is added in the vitriol oil with 3g/L, and under 80 ℃ of conditions, stirring and refluxing 4 hours continues under the room temperature to reflux 1 hour.In gained solution, add deionized water and centrifugal, remove the acid that remains in the solution, be neutral substantially until solution.With dry 12 hours of solution, fully remove residual water-content then.The carbon nanotube powder that obtains is ground 15min, obtain the acidifying carbon nanotube.1.5gPHBV (containing PHV79%) is dissolved in the 60ml chloroform, and 50 ℃ of water-baths are back to abundant dissolving.Add the carbon nanotube 0.0045g after tensio-active agent is handled, ultra-sonic dispersion 10min.Mould is poured scattered solution in the culture dish into after preheating under 40 ℃ the temperature, leaves standstill 2min.Evaporate a large amount of solvents in earlier under 70 ℃ of conditions, then drying and moulding at room temperature.
Example two:
Under the room temperature, compound concentration is the 0.002g/mL polyvinylpyrrolidone aqueous solution, 40 ℃ of water-bath dissolvings.Add 0.7g carbon nanotube (multi-walled carbon nano-tubes, internal diameter 40-60nm, length 5-15 μ m), ultra-sonic dispersion 15min.With the mixed solution centrifugation, remove water layer, and place vacuum drying oven.Thorough drying is ground to constant weight, obtains the surface active carbon nanotube.The 1.5g poly(lactic acid) is dissolved in the 60ml acetone, and 40 ℃ of water-baths are to fully dissolving.Add the carbon nanotube 0.0075g after tensio-active agent is handled, ultra-sonic dispersion 10min.Mould is after preheating under 30 ℃ the temperature, and scattered solution is poured in the culture dish, leaves standstill 3min. and earlier evaporates a large amount of solvents at 5 ℃, then drying and moulding at room temperature.
Example three:
Carbon nanotube (Single Walled Carbon Nanotube, internal diameter≤2nm, length 1-2 μ m) is added in the concentrated nitric acid solution with 3.5g/L, and under 90 ℃ of conditions, stirring and refluxing 3.5 hours continues under the room temperature to reflux 2 hours.In gained solution, add deionized water and centrifugal, remove the acid that remains in the solution, be neutral substantially until solution.With dry 12 hours of solution, fully remove residual water-content then.The carbon nanotube powder that obtains is ground 15min, obtain the acidifying carbon nanotube.Poly-oneself the interior acid esters of 1.5g is dissolved in the 60ml dimethylbenzene, and 60 ℃ of water-baths are back to abundant dissolving.Add the carbon nanotube 0.0075g after tensio-active agent is handled, ultra-sonic dispersion 10min.Mould is after preheating under 50 ℃ the temperature, and scattered solution is poured in the culture dish, leaves standstill 2min.Drying and moulding under the room temperature.
Example four:
Carbon nanotube (multi-walled carbon nano-tubes, internal diameter 80-100nm, length 1-2 μ m) is added with 3.5g/L in the mixing acid of sulfuric acid and nitric acid, and under 90 ℃ of conditions, stirring and refluxing 3.5 hours continues under the room temperature to reflux 3 hours.In gained solution, add deionized water and centrifugal, remove the acid that remains in the solution, be neutral substantially until solution.With dry 20 hours of solution, fully remove residual water-content then.The carbon nanotube powder that obtains is ground 15min, obtain the carboxylic acid carbon nano tube.1.5gPHBV (containing PHV36%) is dissolved in the 60ml chloroform, and 60 ℃ of water-baths are back to abundant dissolving.Add the carbon nanotube 0.015g after tensio-active agent is handled, ultra-sonic dispersion 10min.Mould is after preheating under 60 ℃ the temperature, and scattered solution is poured in the culture dish, leaves standstill 2min.Evaporate a large amount of solvents in earlier under 70 ℃ of conditions, then drying and moulding at room temperature.Through omnipotent mechanics tensile testing machine test, identical with composition, the sample that does not add carbon nanotube is compared, and the Young's modulus and the tensile strength of matrix material all are significantly improved.Among Fig. 1, curve 1 is the stress-strain(ed) curve of polyhydroxybutyrate valerate, curve 2 is stress-strain(ed) curves that the acidifying carbon nanotube strengthens polyhydroxybutyrate valerate matrix material, Fig. 2 is the Young's modulus of compound front and back material, as seen from the figure, when content of carbon nanotubes was 1wt%, the Young's modulus of matrix material has improved by 144.9MPa brought up to 297MPa, and tensile strength has improved by 3.87MPa brings up to 6.97MPa.
Example five:
Under the room temperature, compound concentration is the 0.04g/mL sodium dodecyl benzene sulfonate aqueous solution, 50 ℃ of water-bath dissolvings.Add 0.7g carbon nanotube (multi-walled carbon nano-tubes, internal diameter 80-100nm, length 1-2 μ m), ultra-sonic dispersion 15min.With the mixed solution centrifugation, remove water layer, and place vacuum drying oven.Thorough drying is ground to constant weight, obtains the surface active carbon nanotube.The 1.5g polyglycolic acid is dissolved in the 60ml methylene dichloride, and 50 ℃ of water-baths are to fully dissolving.Add the carbon nanotube 0.0045g after tensio-active agent is handled, ultra-sonic dispersion 15min.Mould is after preheating under 40 ℃ the temperature, and scattered solution is poured in the culture dish, leaves standstill 1min.In loft drier, evaporate earlier a large amount of solvents, then drying and moulding at room temperature.
Claims (8)
1. the preparation method of a degradable biocompatibility macromolecule/carbon nano-tube composite material is characterized in that, preparation process is as follows:
1) surface active of carbon nanotube
Optional following a kind of method:
Method 1: carbon nanotube is added in the strong acid solution with 1-15g/L, under the 70-140 ℃ of condition, stirring and refluxing 3-12 hour, continue backflow 1-4 hour under the room temperature, removal remains in the acid in the solution, is neutral until solution, then with dry 12-24 hour of solution, the carbon nanotube that obtains is ground 10-60min, obtain carboxylic carbon nano-tube;
Method 2: under the room temperature, analytical pure tensio-active agent etc. is joined solution for 0.001-5g/mL, be stirred to dissolving fully, carbon nanotube is added in this surfactant soln at 20-80 ℃ of heating in water bath, with ultra-sonic dispersion instrument batch process 1-60min, the weight percent of tensio-active agent and carbon nanotube is 0.5%-10%, with the mixed solution centrifugation, removes water layer, and place vacuum drying oven, thorough drying is ground to constant weight, obtains the surface active carbon nanotube;
2) dispersion of carbon nano-tube/polymer complex phase solution
Polymkeric substance is added in the organic solvent, concentration is 1-100mg/ml, in 50-90 ℃ water-bath, be back to dissolving fully, add carboxylic carbon nano-tube and surface active carbon nanotube that step 1 obtains, the carbon nanotube mass percent that adds is 0.01%-20%, ultra-sonic dispersion 2-60min obtains uniform carbon nano-tube/polymer complex phase solution;
3) casting and thermal treatment
The complex phase solution casting of step 2 gained in the mould of preheating, is left standstill 1-5min, gets rid of the bubble in the solution, under-5-90 ℃ condition in solvent evaporated, drying and moulding then.
2. the preparation method of macromolecule/carbon nano-tube composite material as claimed in claim 1 is characterized in that, removing the acid that remains in the solution is to add deionized water, centrifugation then in strong acid solution.
3. the preparation method of macromolecule/carbon nano-tube composite material as claimed in claim 1 is characterized in that, described carbon nanotube is a Single Walled Carbon Nanotube, external diameter scope≤2nm, length 1-15 μ m, perhaps multi-walled carbon nano-tubes, external diameter scope 5-100nm, length 1-15 μ m.
4. the preparation method of macromolecule/carbon nano-tube composite material as claimed in claim 1, it is characterized in that strong acid is the vitriol oil, or concentrated nitric acid, or the mixing acid of the sulfuric acid of 1/100-100/1 volume ratio and nitric acid, or the mixing acid of the hydrochloric acid of 1/100-100/1 volume ratio and nitric acid.
5. the preparation method of macromolecule/carbon nano-tube composite material as claimed in claim 1 is characterized in that, the ultrasonic power of ultra-sonic dispersion is 50-450W.
6. the preparation method of macromolecule/carbon nano-tube composite material as claimed in claim 1 is characterized in that, described tensio-active agent is a kind of in polyvinylpyrrolidone, benzene sulfonic acid sodium salt, sodium sulfonate, calcium sulphonate, ammonium sulphonate, sodium sulfate, the trimethyl-glycine.
7. macromolecule/carbon nano-tube composite material preparation method as claimed in claim 1, it is characterized in that, polymkeric substance described in the step 2 is polyglycolic acid, poly(lactic acid), PHA, poly-a kind of in acid esters, poly-acid anhydrides, polyamino acid, the polyphosphonitrile in oneself, and described organic solvent is a kind of in methylene dichloride, chloroform, tetrahydrofuran (THF), dimethylbenzene, the acetone.
8. the preparation method of macromolecule/carbon nano-tube composite material as claimed in claim 1 is characterized in that, the thickness of the film that obtains after the moulding is 5-300 μ m.
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