CN101239716B - Preparation method of polymer grafting magnetic carbon nano-tube - Google Patents
Preparation method of polymer grafting magnetic carbon nano-tube Download PDFInfo
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- CN101239716B CN101239716B CN2008100641344A CN200810064134A CN101239716B CN 101239716 B CN101239716 B CN 101239716B CN 2008100641344 A CN2008100641344 A CN 2008100641344A CN 200810064134 A CN200810064134 A CN 200810064134A CN 101239716 B CN101239716 B CN 101239716B
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Abstract
The present invention provides a preparing method of polymer graft magnetic carbon nanotube, relating to a preparing method of carbon nanotube. The invention resolves the problem of lower dispersivity and poor wettability of the present carbon nanotube. The preparing method includes following steps: adding organic iron to carbon nanotube polylol solution, cooling to room temperature by heating to boiling, the product dispersing in toluol or chloroform via being separated, dried after adding nonpolar solvent, then adding the prepared solution to solution prepared by L-lactide and evocating agent, then separating, drying product. An applied magnetic field controls the prepared polymer graft magnetic carbon nanotube, and enhances the dispersivity, maximum amplitude of polymer graft magnetic carbon nanotube prepared by tension test as a Polylactide composite material of reinforcement relative to the tensile-strength of the pure polylactic acid is 70%, the wettability between polymer graft magnetic carbon nanotube and polylactic acid is enhanced.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanotube.
Background technology
In biomedical materials field, carbon nanotube can effectively improve tissue engineering bracket and bone fracture internal fixation material mechanical property, can be used as in the drug delivery system pharmaceutical carrier and also under the effect of electromagnetic field carbon nanotube can the induce tissue cell growth.But in actual application, the biocompatibility of carbon nanotube is poor, the dispersiveness in matrix is low and and matrix between the wettability difference become the obstruction of its peculiar function of performance.Research at present mainly concentrates on the problem that improves the dispersed of carbon nanotube or improve the wettability between carbon nanotube and the macromolecule matrix.
Summary of the invention
The problem that the objective of the invention is and wettability difference low for the dispersiveness that solves existing carbon nanotube provides a kind of preparation method of polymer grafting magnetic carbon nano-tube.
Preparation method's step of polymer grafting magnetic carbon nano-tube of the present invention is as follows: be that 1: 300～900 proportioning adds carbon nanotube in the polyvalent alcohol by carbon nanotube and polyvalent alcohol mass ratio one,, ultra-sonic dispersion 5～30 minutes makes the carbon nanotube polyhydric alcohol solutions; Be that 1: 1～4 ratio joins organic iron in the carbon nanotube polyhydric alcohol solutions in the carbon nanotube mass ratio in organic iron and the carbon nanotube polyhydric alcohol solutions then, speed with 1～10 ℃/minute behind mixing under the condition of nitrogen protection is heated to boiling, and keep seething with excitement 10 minutes～12 hours, make reaction solution be cooled to room temperature then, by the mass ratio of the volume of non-polar solvent and the carbon nanotube in the carbon nanotube polyhydric alcohol solutions is that 10: 1 proportioning adds non-polar solvent, with magnet product being assembled separates, drying is 8～12 hours under 50～80 ℃ condition, obtain magnetic carbon nano-tube, mix by the proportioning that with the quality of gained magnetic carbon nano-tube and volume of organic solvent ratio is 1: 2, ultra-sonic dispersion 5-30 minute, organic solvent was toluene or trichloromethane; Two, under the condition of nitrogen protection; be after 2000～8000: 1 the mixed with L-rac-Lactide and initiator according to mol ratio; be warming up to 100～180 ℃ with 5～10 ℃/minute speed; the solution that adds the step 1 preparation then; make that the mass ratio of magnetic carbon nano-tube and rac-Lactide is 1: 1～6 in the solution of step 1 preparation, stir and be incubated 12～48 hours, wash product five to eight times with organic solvent; use the magnetic field separation reaction product, drying is 8～12 hours under 40～80 ℃ temperature.
Carbon nanotube in the step 1 of the present invention is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube, polyvalent alcohol is a triglycol, organic iron is praseodynium iron, diacetyl acetone iron, ferric acetyl acetonade, pentacarbonyl iron, iron octoate, ironic oxalate or ironic acetate, and non-polar solvent is ethyl acetate, acetone or normal hexane.
Initiator in the step 2 is a stannous octoate, organic solvent is trichloromethane, methylene dichloride, tetrahydrofuran (THF), N, dinethylformamide, toluene, ethylene glycol, propylene glycol, Isopropanediol, glycerol, glycol ether, Triethylene glycol, tetraethylene-glycol or polyoxyethylene glycol; Be 2000～8000: 1 mixed with the mixture of a kind of composition in L-rac-Lactide and DL-rac-Lactide, glycollide, 6-caprolactone, ethylene glycol, dioxane hexanedione and the oxygen ethene and initiator according to mol ratio in the step 2, wherein a kind of mass ratio is 1: 1～4 in L-rac-Lactide and DL-rac-Lactide, glycollide, 6-caprolactone, ethylene glycol, dioxane hexanedione and the oxygen ethene.
Externally-applied magnetic field can be controlled the direction of the polymer grafting magnetic carbon nano-tube of the present invention's preparation, so when the preparation matrix material, can control its dispersiveness by changing externally-applied magnetic field.So the magnetic carbon nano-tube of polymer graft has superparamagnetism can influence middle hydrogen nuclei in the human body under the effect in magnetic field magnetic moment, thereby found out by nucleus magnetic resonance, can effectively in human body, effectively monitor the accuracy of drug targeting and functional (space hold facility, the cell growing state etc.) of tissue engineering bracket.The polymer grafting magnetic carbon nano-tube that draws the present invention's preparation by tensile strength test is 70% with respect to the maximum amplification of pure state poly(lactic acid) tensile strength, make the mechanical property of polymer grafting magnetic carbon nano-tube be largely increased, its reason is because the wettability of polymer grafting magnetic carbon nano-tube/lactic acid composite material is improved.
The polymer grafting magnetic carbon nano-tube of the present invention preparation is at the surface grafting polymerization thing, and magnetic carbon nano-tube do not had any destruction, kept the magnetic carbon nano-tube original physical characteristics.
Description of drawings
Fig. 1 is the graph of a relation between matrix material tensile strength and the carbon nanotube percentage composition, A represents the pure state poly(lactic acid) among the figure, B represents that the carbon nanotube mass content is 0.5% carbon nano-tube/poly lactic acid composite, B1 represents that the carbon nanotube mass content is 1% carbon nano-tube/poly lactic acid composite, B2 represents that the carbon nanotube mass content is 2% carbon nano-tube/poly lactic acid composite, C represents that the polymer grafting magnetic carbon nano-tube mass content is polymer grafting magnetic carbon nano-tube/lactic acid composite material of 0.5%, C1 represents that the polymer grafting magnetic carbon nano-tube mass content is polymer grafting magnetic carbon nano-tube/lactic acid composite material of 1%, and C2 represents that the polymer grafting magnetic carbon nano-tube mass content is polymer grafting magnetic carbon nano-tube/lactic acid composite material of 2%.Fig. 2 be magneticstrength when being 0mT polymer grafting magnetic carbon nano-tube in the orientation maps in magnetic field.Fig. 3 be magneticstrength when being 174mT polymer grafting magnetic carbon nano-tube in the orientation maps in magnetic field.Fig. 4 is a poly(lactic acid) grafting magnetic carbon nano-tube transmission electron microscope photo.Fig. 5 is the pure state magnetic carbon nano-tube transmission electron microscope photo that does not have polymer graft.
Embodiment
Embodiment one: preparation method's step of polymer grafting magnetic carbon nano-tube is as follows in the present embodiment: be that 1: 300～900 proportioning adds carbon nanotube in the polyvalent alcohol by carbon nanotube and polyvalent alcohol mass ratio one,, ultra-sonic dispersion 5～30 minutes makes the carbon nanotube polyhydric alcohol solutions; Be that 1: 1～4 ratio joins organic iron in the carbon nanotube polyhydric alcohol solutions in the carbon nanotube mass ratio in organic iron and the carbon nanotube polyhydric alcohol solutions then, speed with 1～10 ℃/minute behind mixing under the condition of nitrogen protection is heated to boiling, and keep seething with excitement 10 minutes～12 hours, make reaction solution be cooled to room temperature then, by the mass ratio of the volume of non-polar solvent and the carbon nanotube in the carbon nanotube polyhydric alcohol solutions is that 10: 1 proportioning adds non-polar solvent, with magnet product being assembled separates, drying is 8～12 hours under 50～80 ℃ condition, obtain magnetic carbon nano-tube, mix by the proportioning that with the quality of gained magnetic carbon nano-tube and volume of organic solvent ratio is 1: 2, ultra-sonic dispersion 5-30 minute, organic solvent was toluene or trichloromethane; Two, under the condition of nitrogen protection; be after 2000～8000: 1 the mixed with L-rac-Lactide and initiator according to mol ratio; be warming up to 100～180 ℃ with 5～10 ℃/minute speed; the solution that adds the step 1 preparation then; make that the mass ratio of magnetic carbon nano-tube and rac-Lactide is 1: 1～6 in the solution of step 1 preparation, stir and be incubated 12～48 hours, wash product five to eight times with organic solvent; use the magnetic field separation reaction product, drying is 8～12 hours under 40～80 ℃ temperature.
After in the step 1 mixed solution of organic iron and carbon nanotube polyhydric alcohol solutions being heated to boiling, organic iron resolves into monocrystalline ferriferrous oxide nano-particle or monocrystalline ferric oxide nanoparticles and the self-assembly surface at carbon nanotube.
Present embodiment with polymer grafting magnetic carbon nano-tube and carbon nanotube as strengthening body, poly(lactic acid) is a matrix, utilize solvent evaporated method to prepare matrix material, be carbon nano-tube/poly lactic acid composite and polymer grafting magnetic carbon nano-tube/lactic acid composite material, the tensile strength of carbon nano-tube/poly lactic acid composite and polymer grafting magnetic carbon nano-tube/lactic acid composite material has been carried out contrast as shown in Figure 1, when the mass percent that strengthens body is 2%, the fracture tensile strength of polymer grafting magnetic carbon nano-tube/lactic acid composite material has improved 70% than the pure state poly(lactic acid), Young's modulus has improved 80%, and tension set changes very little.Polymer grafting magnetic carbon nano-tube/lactic acid composite material is 70% with respect to the maximum amplification of pure state poly(lactic acid) tensile strength, and the tensile strength of carbon nano-tube/poly lactic acid composite is very little and be to reduce on the contrary in 2% o'clock in the carbon nanotube mass content with respect to pure state poly(lactic acid) amplification, has good interface binding power between this explanation polymer grafting magnetic carbon nano-tube and the poly(lactic acid), the mechanical property of polymer grafting magnetic carbon nano-tube/lactic acid composite material is largely increased, and its reason is that the wettability of polymer grafting magnetic carbon nano-tube/lactic acid composite material improves.
In the present embodiment 5mg magnetic carbon nano-tube is dissolved in 20ml ethanol or the trichloromethane, after ultrasonic 30 minutes, mixed solution is dropped on the silicon chip in field emission scanning electron microscope (scanning electron microscope model: the S-4700 of Hitachi) observe down with drop-burette.As can be seen from Figure 2 polymer grafting magnetic carbon nano-tube at random being dispersed on the silicon chip when magneticstrength is 0mT, as can be seen from Figure 3 variation has taken place in the directivity of polymer grafting magnetic carbon nano-tube when magnetic field becomes 174mT by 0mT, clearly, polymer grafting magnetic carbon nano-tube all tilts to the direction that becomes 45 degree with horizontal plane, and this direction is a field direction.Therefore, this result shows that polymer grafting magnetic carbon nano-tube aligns under externally-applied magnetic field, and externally-applied magnetic field can be controlled the direction of magnetic carbon nano-tube, when the preparation matrix material, can control its dispersiveness by changing externally-applied magnetic field then.
Present embodiment is with poly(lactic acid) grafting carbon nanotube transmission electron microscope photo (Fig. 4) and do not have the pure state magnetic carbon nano-tube transmission electron microscope photo (Fig. 5) of polymer graft to compare, there is a lot of flosss to be attached on the carbon nanotube tube wall as can be seen from Figure 4, the globe that also has a lot of black on the tube wall, these flosss and globe are respectively poly(lactic acid) and magnetic-particle, because polymkeric substance in the outer wall grafting, carbon nanotubes lumen is smudgy, and the caliber of carbon nanotube is thick than the pure state magnetic carbon nano-tube caliber that does not have polymer graft among Fig. 5, the magnetic-particle of black is evenly adhered on the pure state magnetic carbon nano-tube surface that does not have polymer graft among Fig. 5, and carbon nanotubes lumen is high-visible.This shows that preparation polymer grafting magnetic carbon nano-tube method related among the present invention can obtain comparatively evenly graftomer on the magnetic carbon nano-tube surface, and magnetic carbon nano-tube is not had any destruction, kept the magnetic carbon nano-tube original physical characteristics.
Embodiment two: present embodiment and embodiment one are different is that carbon nanotube in the step 1 is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one are different is that polyvalent alcohol in the step 1 is a triglycol.Other is identical with embodiment one.
Embodiment four: present embodiment and embodiment one are different is that organic iron in the step 1 is praseodynium iron, diacetyl acetone iron, ferric acetyl acetonade, pentacarbonyl iron, iron octoate, ironic oxalate or ironic acetate.Other is identical with embodiment one.
Embodiment five: present embodiment and embodiment one are different is that the carbon nanotube in the carbon nanotube polyhydric alcohol solutions and organoferric mass ratio are 1: 3 in the step 1.Other is identical with embodiment one.
Embodiment six: present embodiment and embodiment one are different is that the mass ratio of carbon nanotube and polyvalent alcohol is 1: 301～600 in the step 1.Other is identical with embodiment one.
Embodiment seven: present embodiment and embodiment one are different is that the mass ratio of carbon nanotube and polyvalent alcohol is 1: 601～899 in the step 1.Other is identical with embodiment one.
Embodiment eight: present embodiment and embodiment one are different is that the mass ratio of carbon nanotube and polyvalent alcohol is 1: 500 in the step 1.Other is identical with embodiment one.
Embodiment nine: present embodiment and embodiment one are different is that non-polar solvent in the step 1 is ethyl acetate, acetone or normal hexane.Other is identical with embodiment one.
Embodiment ten: present embodiment and embodiment one are different is that initiator in the step 2 is a stannous octoate.Other is identical with embodiment one.
Embodiment 11: present embodiment and embodiment one are different is that solvent in the step 2 is trichloromethane, methylene dichloride, tetrahydrofuran (THF), N, dinethylformamide, toluene, ethylene glycol, propylene glycol, Isopropanediol, glycerol, glycol ether, Triethylene glycol, tetraethylene-glycol or polyoxyethylene glycol.Other is identical with embodiment one.
Embodiment 12: present embodiment and embodiment one are different is that the mol ratio of L-rac-Lactide and initiator is 3000: 1 in the step 2.Other is identical with embodiment one.
Embodiment 13: present embodiment and embodiment one are different is that the mol ratio of L-rac-Lactide and initiator is 5000: 1 in the step 2.Other is identical with embodiment one.
Embodiment 14: present embodiment and embodiment one are different is in the step 2 to be 2000～8000: 1 mixed according to mol ratio with the mixture of a kind of composition in L-rac-Lactide and DL-rac-Lactide, glycollide, 6-caprolactone, ethylene glycol, dioxane hexanedione and the oxygen ethene and initiator.Other is identical with embodiment one.
Embodiment 15: what present embodiment and embodiment 14 were different is that mass ratio a kind of in L-rac-Lactide and DL-rac-Lactide, glycollide, 6-caprolactone, ethylene glycol, dioxane hexanedione and the oxygen ethene is 1: 1～4.Other is identical with embodiment 14.
Embodiment 16: present embodiment and embodiment one are different is that the mixture of a kind of composition in L-rac-Lactide and DL-rac-Lactide, glycollide, 6-caprolactone, ethylene glycol, dioxane hexanedione and the oxygen ethene in the step 2 and the mol ratio of initiator are 3000: 1.Other is identical with embodiment 14.
Embodiment 17: present embodiment and embodiment one are different is that the mixture of a kind of composition in L-rac-Lactide and DL-rac-Lactide, glycollide, 6-caprolactone, ethylene glycol, dioxane hexanedione and the oxygen ethene in the step 2 and the mol ratio of initiator are 5000: 1.Other is identical with embodiment 14.
Claims (3)
1. the preparation method of a polymer grafting magnetic carbon nano-tube, the preparation method's step that it is characterized in that polymer grafting magnetic carbon nano-tube is as follows: be that 1: 300～900 proportioning adds carbon nanotube in the polyvalent alcohol by carbon nanotube and polyvalent alcohol mass ratio one,, ultra-sonic dispersion 5～30 minutes makes the carbon nanotube polyhydric alcohol solutions; Be that 1: 1～4 ratio joins organic iron in the carbon nanotube polyhydric alcohol solutions in the carbon nanotube mass ratio in organic iron and the carbon nanotube polyhydric alcohol solutions then, speed with 1～10 ℃/minute behind mixing under the condition of nitrogen protection is heated to boiling, and keep seething with excitement 10 minutes～12 hours, make reaction solution be cooled to room temperature then, by the mass ratio of the volume of non-polar solvent and the carbon nanotube in the carbon nanotube polyhydric alcohol solutions is that 10: 1 proportioning adds non-polar solvent, with magnet product being assembled separates, drying is 8～12 hours under 50～80 ℃ condition, obtain magnetic carbon nano-tube, mix by the proportioning that with the quality of gained magnetic carbon nano-tube and volume of organic solvent ratio is 1: 2, ultra-sonic dispersion 5-30 minute, organic solvent was toluene or trichloromethane; Two, under the condition of nitrogen protection, be after 2000～8000: 1 the mixed with L-rac-Lactide and initiator according to mol ratio, be warming up to 100～180 ℃ with 5～10 ℃/minute speed, the solution that adds the step 1 preparation then, make that the mass ratio of magnetic carbon nano-tube and rac-Lactide is 1: 1～6 in the solution of step 1 preparation, stir and be incubated 12～48 hours, wash product five to eight times with organic solvent, use the magnetic field separation reaction product, drying is 8～12 hours under 40～80 ℃ temperature; Polyvalent alcohol in the step 1 is a triglycol; Organic iron in the step 1 is praseodynium iron, diacetyl acetone iron, ferric acetyl acetonade, pentacarbonyl iron, iron octoate, ironic oxalate or ironic acetate; Non-polar solvent in the step 1 is ethyl acetate, acetone or normal hexane; Initiator in the step 2 is a stannous octoate.
2. the preparation method of polymer grafting magnetic carbon nano-tube according to claim 1 is characterized in that the carbon nanotube in the step 1 is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
3. the preparation method of polymer grafting magnetic carbon nano-tube according to claim 1, it is characterized in that the organic solvent in the step 2 is trichloromethane, methylene dichloride, tetrahydrofuran (THF), N, dinethylformamide, toluene, ethylene glycol, propylene glycol, Isopropanediol, glycerol, glycol ether, Triethylene glycol, tetraethylene-glycol or polyoxyethylene glycol.
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| CN110482530B (en) * | 2019-09-04 | 2020-12-29 | 北京华碳元芯电子科技有限责任公司 | Method for preparing patterned carbon nanotube film |
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| CN1569623A (en) * | 2004-04-22 | 2005-01-26 | 华中师范大学 | Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly |
| CN1670251A (en) * | 2005-03-01 | 2005-09-21 | 东华大学 | Method for preparing magnetic compound material of ferric oxide cladded carbon nanotube |
| CN1736858A (en) * | 2005-07-14 | 2006-02-22 | 上海交通大学 | Carbon nanometer tube with surface connected with magnetic nanometer particle and its preparation method |
| CN1971780A (en) * | 2005-11-23 | 2007-05-30 | 北京化工大学 | Preparing method of nano-Fe3O4 coating carbon nanotube magnetic composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569623A (en) * | 2004-04-22 | 2005-01-26 | 华中师范大学 | Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly |
| CN1670251A (en) * | 2005-03-01 | 2005-09-21 | 东华大学 | Method for preparing magnetic compound material of ferric oxide cladded carbon nanotube |
| CN1736858A (en) * | 2005-07-14 | 2006-02-22 | 上海交通大学 | Carbon nanometer tube with surface connected with magnetic nanometer particle and its preparation method |
| CN1971780A (en) * | 2005-11-23 | 2007-05-30 | 北京化工大学 | Preparing method of nano-Fe3O4 coating carbon nanotube magnetic composite material |
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