CN101693125A - Process for preparing biocompatible directional carbon nanotube array reinforced composite hydrogel - Google Patents
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Abstract
The invention provides a process for preparing biocompatible directional carbon nanotube array reinforced composite hydrogel, which utilizes the chemical vapor deposition (CVD) technique, the radial cross linking technique and a freezing and thawing method. By permeating polymer sol into a carbon nanotube prefabricated body, aggregating and tangling problems during a compounding process of the carbon nanotube and polymer are resolved, boundary strength of a reinforcing phase and a basis phase is increased, and excellent performances of the nanotube on mechanics and electricity are played sufficiently. The composite hydrogel prepared by utilizing a physical cross linking process does not contain chemical additives and meets requirements on biocompatibility. The composite hydrogel prepared by the process has controllable length and direction of the reinforcing phase of a nanotube array, has integrated mechanics and electricity performances superior to those of the conventional hydrogel, and is adoptive to be applied to the biomedical field such as artificial articular cartilages, tissues engineering supports, nerve cell carries, biomimetic implanted electrode and the like.
Description
Technical field
The present invention relates to biomedical materials field, particularly the preparation of directional carbon nanotube array reinforced composite hydrogel.
Background technology
Hydrogel be can be in water swelling and keep large quantity of moisture and undissolvable cross linked polymer.They can be swelling to the balance volume rapidly in water, still can keep its shape and three-dimensional space network structure, and the deswelling of dewatering under certain condition, are that a class set suction, water conservation, slow release are in the functional high molecule material of one.Owing to contain large quantity of moisture in the cross-linked network, hydrogel is extremely similar to biological tissue, its softness, moistening the surface and with the tissue affinity significantly reduced the stimulation of material to surrounding tissue, make hydrogel have excellent biological compatibility and histocompatibility.Therefore, hydrogel is very extensive in the purposes of biomedical aspect, can be used as microorganism immobilization carrier, medicinal slow release agent, contact lenses, artificial blood plasma, artificial skin, tissue engineering bracket material etc.
CNT 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 draw ratio is generally greater than 1000.Because CNT has the structure of sealing, so the axial strength that it had and elastic modelling quantity are high, and higher more than 100 times than the intensity of steel, theoretical Young's modulus can be up to 1.8 * 10
12Pa, and proportion has only 1/6～1/7 of steel, is the material that has high specific strength at present.CNT has basic effects such as skin effect that general nano material has, small-size effect, and has performances such as excellent mechanics, electricity, optics, magnetics, calorifics, is suitable as very much the reinforcing material of other materials.It is acidproof, alkaline-resisting, high temperature resistant for what is more important, has higher chemical stability and excellent biological compatibility, and as bio-medical material, it is very favourable being applied to the human internal environment for CNT for this.
Strengthen composite aquogel by the preparation CNT, can be when keeping the hydrogel good biocompatibility, improve its mechanical property and electric property greatly, the bio-medical material of obtained performance excellence, enlarge hydrogel drug release carrier, various soft/application of aspects such as hard tissue regeneration reparation and organizational project organ culture.
CNT has skin effect and bulk effect, its granule is little, specific surface area is big, has very strong Van der Waals force between pipe, be easy to form aggregate, thereby with the recombination process of polymer in agglomeration usually appears, combine with polymer not tight, thereby influenced the reinforced effects of CNT in matrix and the performance of performance.Existing carbon nanotube chemical modification and purification process technology all fail effectively to solve this difficult problem.And, need the aligned carbon nanotube film of overlength, successive CNT long filament and Centimeter Level area in many important use occasions, just can give full play to performances such as CNT unique mechanical, electricity, calorifics.In addition, the preparation method and the application in the bio-medical field thereof of aligned carbon nanotube enhancing hydrogel composite material yet there are no bibliographical information so far.
Summary of the invention
The preparation method that the purpose of this invention is to provide a kind of biocompatible directional carbon nanotube array reinforced composite hydrogel, make the directional carbon nanotube array reinforced composite hydrogel of preparing when keeping inherent biocompatibility of hydrogel and histocompatibility, improve its mechanical property and electric property, and can regulate and control above-mentioned performance according to instructions for use.
The present invention adopts chemical vapor deposition (CVD) technology, crosslinking with radiation technology and freeze-thaw legal system to be equipped with directional carbon nanotube array reinforced composite hydrogel.Processing step is as follows:
Step 1: preparation directional carbon nanotube array
Adopt the chemical vapor deposition (CVD) technology to prepare directional carbon nanotube array.The heating of employing resistance furnace uses quartz glass tube as reactor.With the growth substrate of quartz glass plate as aligned carbon nanotube, be equipped on the quartz boat, place in the middle of the reative cell.Carbon source, catalyst and carrier gas (hydrogen and argon) are introduced from an end of quartz ampoule, and tail gas is discharged from the other end.Carbon source is carbon monoxide or Hydrocarbon such as methane, ethane, ethylene, propylene etc., with the flow of mass flowmenter control valve control carbon source.If working load type catalyst needs in advance catalyst to be coated onto in the substrate; If use floating catalyst, then need a spraying system (as accurate flow pump) with the catalyst injection of gasification in the carbon source air-flow.Usually the growing method of aligned carbon nanotube is to reach reaction temperature with argon or other inert gas purge reactor to reactors earlier, then gas is switched to carbon source, after the directional carbon nanotube array growth finishes, gas is switched back noble gas and is cooled to room temperature, take out sample.The CNT of preparing in this way is generally multi-walled carbon nano-tubes, and (external diameter scope 5～100nm), the growth length of CNT depends on the supply of carbon source, even its growth length can reach 6mm.
Step 2: preparation polymeric sol
Analytically pure high molecular polymer is added in the redistilled water, be mixed with the high molecular polymer mass fraction and be 5～40% aqueous solution, in 50～95 ℃ of waters bath with thermostatic control, be stirred to the solid polymer uniform dissolution, perhaps put into the dissolving of steam vessel in heating, container inner pressure maintains 0.08～0.12MPa, temperature is 100～120 ℃, 0.5～2 hour heat time heating time.At last, will dissolve uniform polymeric sol and leave standstill cooling at room temperature, drain to bubble.
Described high molecular polymer is the avirulent high molecular polymer that is suitable for biomedicine field, can be polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), Polyethylene Glycol (PEG), polyacrylamide (PAM), polyacrylic acid (PAA), polyvinyl methyl ether (PVME), polyethylene glycol oxide (PEO), chitosan (chitosan), water-soluble chitosan (ws-chitin), collagen (collagen), gelatin (gelatin), hyaluronic acid (HA), a kind of in alginate and the fibrin or by above-mentioned any two kinds of mixture of forming to five kinds of macromolecular materials.
Step 3: polymeric sol is infiltrated in the CNT precast body
To be dispersed in by the directional carbon nanotube array that step 1 makes in the plane mould, in mould, slowly infiltrate polymeric sol again, the mass ratio of CNT and polymeric sol is 0.01/99.99～20/80, makes polymeric sol enveloped carbon nanometer tube precast body, obtains mixture.
Step 4: freeze-thaw method or crosslinking with radiation legal system are equipped with the CNT composite aquogel
Method 1: the mixture that step 3 is obtained carries out the freeze-thaw circular treatment.Cryogenic temperature-35～-5 ℃, cooling time 5～24 hours at room temperature thawed 1～12 hour then, and so the freeze-thaw circulation is 1～8 time, obtains directional carbon nanotube array reinforced composite hydrogel.This method is applicable to that mainly matrix is polyvinyl alcohol (PVA) or the high polymer mixtures that contains polyvinyl alcohol.
Method 2: before carrying out the freeze-thaw circular treatment of method 1 or after it, the hydrogel that mixture that step 3 is obtained or method 1 obtain carries out RADIATION PROCESSING, adopting dosage is gamma-rays, electron beam, X ray or the ultraviolet irradiation mixture of 10～100kGy, by strengthening the chemical crosslinking effect between high molecular polymer, further improve the mechanical strength of hydrogel.This method is applicable to that mainly matrix is polyvinyl alcohol (PVA) or the high polymer mixtures that contains polyvinyl alcohol.
Method 3: adopt gamma-rays, electron beam, X ray or ultraviolet that the mixture that step 3 obtains is carried out RADIATION PROCESSING, dosage is 10～100kGy, obtains directional carbon nanotube array reinforced composite hydrogel.This method is applicable to that matrix is described various high molecular polymers of step 2 and composition thereof.
The directional carbon nanotube array reinforced composite hydrogel thickness that adopts the present invention to make is 10～3000 μ m.The moisture mass percent of matrix phase hydrogel is 60～99%.
The present invention compared with prior art has following advantage and beneficial effect:
Adopt chemical gaseous phase depositing process to prepare directional carbon nanotube array, the growth by the supply control CNT of carbon source reaches the controlled purpose of length of carbon nanotube.Adopt the polymeric sol infiltration method that polymeric sol is infiltrated in the CNT precast body, overcome the reunion entanglement problems that CNT and polymer recombination process occur, the promotion CNT combines with the matrix hydrogel, has improved wild phase and matrix boundary strength mutually.The CNT that aligns in matrix can be given full play to the excellent properties of CNT aspect mechanics, electricity, improves the comprehensive mechanical property and the electric conductivity of hydrogel.Adopt freeze-thaw method and crosslinking with radiation legal system to be equipped with composite aquogel, strengthened the crosslinked action between high molecular polymer, this method does not contain any chemical addition agent simultaneously, and is nontoxic, satisfies the requirement of biocompatibility.In addition, the addition by the control aligned carbon nanotube can change content and the distribution of CNT in matrix; Parameters such as the radiation dose during the control crosslinking with radiation and the temperature of freeze-thaw process, time, cycle-index can change the condensed state structure and the crystallization degree of high molecular polymer, thereby reach the controlled purpose of preparing of composite aquogel performance.
The present invention is fit to be applied to bio-medical fields such as artificial articular cartilage, tissue engineering bracket, neurocyte carrier, bionical implant electrode material.
The specific embodiment
Example 1
Step 1: take by weighing ferrocene powder 5g, be dissolved in the 50mL dimethylbenzene.Form pale brown color clear solution behind the mix homogeneously, left standstill 36 hours.Quartz glass plate is equipped on the quartz boat, slowly pushes chemical vapor deposition unit reative cell middle part, with the two ends of fluid sealant sealing quartz ampoule.Feed argon, flow is 100mL/min, reacting by heating chamber to 900 ℃.The adjustment argon flow amount is 2000mL/min, and feeds the hydrogen of 400mL/min.Mobile quartz ampoule is adjusted the position of capillary tube opening with respect to burner hearth, makes the registration of thermocouple remain on 250～300 ℃, guarantees that reaction solution can be vaporific spraying into.Open accurate flow pump, make ferrocene/dimethylbenzene reactant solution be vaporific by capillary tube and spray in the reative cell, the solution feed speed is 0.4mL/min.Reaction finishes, and stops to feed hydrogen, and the flow of turning argon down makes reative cell be cooled to room temperature in argon gas atmosphere to 100mL/min, takes out sample, obtains directed array of multi-walled carbon nanotubes.
Step 2: polyvinyl alcohol (PVA) solid particle is mixed with redistilled water, make the PVA mass fraction and be 20% PVA aqueous solution, put into the dissolving of steam vessel in heating, container inner pressure maintains 0.1MPa, temperature is 120 ℃, 1.5 hours heat time heating times.To dissolve uniform PVA polymeric sol then and take out, leave standstill cooling.
Step 3: take by weighing a certain amount of directed array of multi-walled carbon nanotubes and be dispersed in the plane mould, the PVA polymeric sol is slowly injected mould by the mold side edge, make it evenly to coat directional carbon nanotube array, the mass percent of CNT and polymeric sol is 0.5/99.5.
Step 4: mould is put into-26 ℃ freezing 10 hours of environment, at room temperature thawed then 4 hours, so circulating frozen thaws 5 times, obtains directed array of multi-walled carbon nanotubes and strengthens polyvinyl alcohol composite hydrogel.
Test result shows that behind the adding CNT, the hot strength of composite aquogel is 5.4MPa, and tearing strength is 9.8kN/m, compares with 4.0kN/m with the 1.2MPa of polyvinyl alcohol hydrogel (not adding CNT), has improved 350% and 145% respectively.Aspect electric property, add CNT after, the high frequency of composite aquogel (＞1000Hz) order of magnitude of electrical impedance is by 10 of polyvinyl alcohol hydrogel
4Drop to 10
3, conductive capability raises.
Example 2
Step 1: take by weighing ferrocene powder 6g, be dissolved in the 50mL dimethylbenzene.Form pale brown color clear solution behind the mix homogeneously, left standstill 30 hours.Quartz glass plate is equipped on the quartz boat, slowly pushes chemical vapor deposition unit reative cell middle part, with the two ends of fluid sealant sealing quartz ampoule.Feed argon, flow is 100mL/min, reacting by heating chamber to 900 ℃.The adjustment argon flow amount is 1000mL/min, and feeds the hydrogen of 150mL/min.Mobile quartz ampoule is adjusted the position of capillary tube opening with respect to burner hearth, makes the registration of thermocouple remain on 200 ℃, guarantees that reaction solution can be vaporific spraying into.Open accurate flow pump, make ferrocene/dimethylbenzene reactant solution be vaporific by capillary tube and spray in the reative cell, the solution feed speed is 0.4mL/min.Reaction finishes, and stops to feed hydrogen, and the flow of turning argon down makes reative cell be cooled to room temperature in argon gas atmosphere to 100mL/min, takes out sample.Obtain directed array of multi-walled carbon nanotubes.
Step 2: analytically pure polyvinylpyrrolidone (PVP) granule is added in the redistilled water, be mixed with the PVP mass percent and be 8% aqueous solution, in 60 ℃ of waters bath with thermostatic control, stir, obtain the PVP polymeric sol to the PVP dissolving.
Step 3: take by weighing a certain amount of directed array of multi-walled carbon nanotubes and be dispersed in the flat glass culture dish, the PVP polymeric sol is slowly injected by the culture dish edge, make it evenly to coat directional carbon nanotube array, the mass percent of CNT and polymeric sol is 5/95.
Step 4: culture dish sealing is placed on carries out radiation treatment in the radiation field, dosage 20kGy obtains directed array of multi-walled carbon nanotubes and strengthens the polyvinylpyrrolidone composite aquogel.
Test result shows that behind the CNT that adding aligns, the coefficient of friction of composite aquogel drops to 0.09 by 0.25 of matrix hydrogel (not adding CNT), and the greasy property of hydrogel improves.And the elastic modelling quantity of composite aquogel rises to 3.0MPa by 1.0MPa, and hot strength rises to 4.2MPa by 0.7MPa, and comprehensive mechanical property improves.
Example 3
Step 1: the quartz glass plate that will evenly spread the Co/ silica-gel catalyst is equipped on the quartz boat, slowly pushes chemical vapor deposition unit reative cell middle part, with the two ends of fluid sealant sealing quartz ampoule.Feed argon, flow is 100mL/min, reacting by heating chamber to 700 ℃.The adjustment argon flow amount is 1000mL/min, and feeds hydrogen and the acetylene gas mixture of 150mL/min.Reaction finishes, and stops to feed hydrogen and acetylene gas mixture, and the flow of turning argon down makes reative cell be cooled to room temperature in argon gas atmosphere to 100mL/min, takes out sample.Obtain directed array of multi-walled carbon nanotubes.
Step 2: analytically pure polyvinylpyrrolidone (PVP) powder is added in the redistilled water, be mixed with the PVP mass percent and be 5% aqueous solution, in 60 ℃ of waters bath with thermostatic control, stir to PVP and dissolve, in PVP solution, add polyvinyl alcohol (PVA) solid particle, making the quality percentage composition of PVA is 10%, after stirring mixed liquor is put into the dissolving of steam vessel in heating, and container inner pressure maintains 0.1MPa, 120 ℃ of temperature, 1.5 hours heat time heating times.Subsequently polymeric sol is taken out, leave standstill cooling.
Step 3: take by weighing a certain amount of directed array of multi-walled carbon nanotubes and be dispersed in the plane mould, the PVA-PVP polymeric sol is slowly injected mould by the mold side edge, make it evenly to coat directional carbon nanotube array, the mass percent of CNT and polymeric sol is 1.5/98.5.
Step 4: mould is put into-26 ℃ freezing 12 hours of environment, at room temperature thawed then 3 hours, so circulating frozen thaws 6 times, obtains directed array of multi-walled carbon nanotubes and strengthens polyvinyl alcohol polyethylene ketopyrrolidine composite aquogel.
Test result shows that the hot strength of CNT composite aquogel rises to 6.0MPa by the 1.0MPa of matrix hydrogel (not adding CNT), high frequency (＞1000Hz) order of magnitude of electrical impedance is by 10 of matrix hydrogel
4Reduce to 10
3, conductive capability strengthens.
Example 4
Step 1: take by weighing ferrocene powder 7g, be dissolved in the 50mL dimethylbenzene.Form pale brown color clear solution behind the mix homogeneously, left standstill 28 hours.Quartz glass plate is equipped on the quartz boat, slowly pushes chemical vapor deposition unit reative cell middle part, with the two ends of fluid sealant sealing quartz ampoule.Feed argon, flow is 100mL/min, reacting by heating chamber to 900 ℃.The adjustment argon flow amount is 1000mL/min, and feeds the hydrogen of 150mL/min.Mobile quartz ampoule is adjusted the position of capillary tube opening with respect to burner hearth, makes the registration of thermocouple remain on 200 ℃, guarantees that reaction solution can be vaporific spraying into.Open accurate flow pump, make ferrocene/dimethylbenzene reactant solution be vaporific by capillary tube and spray in the reative cell, the solution feed speed is 0.4mL/min.Reaction finishes, and stops to feed hydrogen, and the flow of turning argon down makes reative cell be cooled to room temperature in argon gas atmosphere to 100mL/min, takes out sample.Obtain directed array of multi-walled carbon nanotubes.
Step 2: analytically pure chitosan powder is added in 2% acetum, be mixed with chitosan mass percent and be 8% acid solution, in 50 ℃ of waters bath with thermostatic control, stir, obtain the chitosan acid solution to the chitosan dissolving.
Step 3: take by weighing a certain amount of directed array of multi-walled carbon nanotubes and be dispersed in the flat glass culture dish, chitosan solution is slowly injected by the culture dish edge, make it evenly to coat directional carbon nanotube array, the mass percent of CNT and chitosan solution is 2/98.
Step 4: culture dish sealing is placed on carries out radiation treatment in the radiation field, dosage 30kGy makes chitosan molecule be cross-linked to form gel.
Step 5: the composite aquogel that makes was at room temperature used distilled water immersion 3 days, and refresh the water periodically, make the faintly acid soak become neutrality, obtain directed array of multi-walled carbon nanotubes and strengthen the chitosan composite aquogel.
Example 5
Step 1: take by weighing ferrocene powder 4g, be dissolved in the 50mL dimethylbenzene.Form pale brown color clear solution behind the mix homogeneously, left standstill 25 hours.Quartz glass plate is equipped on the quartz boat, slowly pushes chemical vapor deposition unit reative cell middle part, with the two ends of fluid sealant sealing quartz ampoule.Feed argon, flow is 100mL/min, reacting by heating chamber to 900 ℃.The adjustment argon flow amount is 2000mL/min, and feeds the hydrogen of 400mL/min.Mobile quartz ampoule is adjusted the position of capillary tube opening with respect to burner hearth, makes the registration of thermocouple remain on 250～300 ℃, guarantees that reaction solution can be vaporific spraying into.Open accurate flow pump, make ferrocene/dimethylbenzene reactant solution be vaporific by capillary tube and spray in the reative cell, the solution feed speed is 0.4mL/min.Reaction finishes, and stops to feed hydrogen, and the flow of turning argon down makes reative cell be cooled to room temperature in argon gas atmosphere to 100mL/min, takes out sample, obtains directed array of multi-walled carbon nanotubes.
Step 2: with mass ratio is that 6: 4 polyethylene glycol oxide (PEO) and polyvinyl alcohol (PVA) is dissolved in the redistilled water, the solution of preparation macromolecule mixture mass fraction 15%.Heated and stirred is even, obtains the PEO-PVA mixed solution.
Step 3: take by weighing a certain amount of directed array of multi-walled carbon nanotubes and be dispersed in the flat glass culture dish, the PEO-PVA mixed solution is slowly injected by the culture dish edge, make it evenly to coat directional carbon nanotube array, the mass percent of CNT and mixed solution is 7/93.
Step 4: culture dish is put into-20 ℃ freezing 12 hours of environment, at room temperature thawed then 5 hours, so circulating frozen thaws 4 times.Culture dish after will sealing again places radiation field to carry out electron beam irradiation and handles, and dosage 40kGy obtains directed array of multi-walled carbon nanotubes and strengthens polyethylene glycol oxide/polyvinyl alcohol composite hydrogel.
Claims (4)
1. the preparation method of biocompatible directional carbon nanotube array reinforced composite hydrogel after employing chemical vapour deposition (CVD) CVD method is prepared directional carbon nanotube array, prepares polymeric sol, it is characterized in that,
1) directional carbon nanotube array is dispersed in the plane mould, in mould, slowly infiltrate polymeric sol again, the mass ratio of CNT and polymeric sol is 0.01/99.99～20/80, makes polymeric sol enveloped carbon nanometer tube precast body, obtains mixture;
2) select one of following method preparation CNT composite aquogel:
Method 1: mixture is carried out the freeze-thaw circular treatment, cryogenic temperature-35～-5 ℃, cooling time 5～24 hours at room temperature thawed 1～12 hour then, and so the freeze-thaw circulation is 1～8 time, obtains directional carbon nanotube array reinforced composite hydrogel;
Method 2: before carrying out the freeze-thaw circular treatment of method 1 or after it, the hydrogel that mixture or method 1 are obtained carries out RADIATION PROCESSING, and dosage is 10～100kGy;
Method 3: mixture is carried out RADIATION PROCESSING, and dosage is 10～100kGy, obtains directional carbon nanotube array reinforced composite hydrogel;
Described directional carbon nanotube array reinforced composite hydrogel thickness is 10～3000 μ m, and the water content quality percentage composition of matrix phase hydrogel is 60～99%.
2. preparation method as claimed in claim 1, it is characterized in that, the preparation method of described polymeric sol is that analytically pure high molecular polymer is added in the redistilled water, be mixed with the high molecular polymer mass fraction and be 5～40% aqueous solution, be stirred to the solid polymer uniform dissolution in 50～95 ℃ of waters bath with thermostatic control, perhaps put into the dissolving of steam vessel in heating, container inner pressure maintains 0.08～0.12MPa, temperature is 100～120 ℃, 0.5～2 hour heat time heating time.
3. preparation method as claimed in claim 2, it is characterized in that, described high molecular polymer is the avirulent high molecular polymer that is suitable for biomedicine field, comprises the mixture that a kind of or any two kinds to the five kinds macromolecular materials in polyvinyl alcohol, polyvinylpyrrolidone, Polyethylene Glycol, polyacrylamide, polyacrylic acid, polyvinyl methyl ether, polyethylene glycol oxide, chitosan, water-soluble chitosan, collagen, gelatin, hyaluronic acid, alginate and the fibrin are formed.
4. preparation method as claimed in claim 1 is characterized in that, described radiation source adopts gamma-rays, electron beam, X ray or ultraviolet.
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| CN100389145C (en) * | 2006-09-29 | 2008-05-21 | 北京大学 | Water gel containing natural high molecule and its radiation preparing method |
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