CN101555006B - Preparation method of modified carbon nanotube - Google Patents
Preparation method of modified carbon nanotube Download PDFInfo
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- CN101555006B CN101555006B CN2009100151246A CN200910015124A CN101555006B CN 101555006 B CN101555006 B CN 101555006B CN 2009100151246 A CN2009100151246 A CN 2009100151246A CN 200910015124 A CN200910015124 A CN 200910015124A CN 101555006 B CN101555006 B CN 101555006B
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Abstract
The invention discloses a preparation method of a modified carbon nanotube. The condensation reaction is performed to an acidified carbon nanotube and the free radical of nitroxide of 4- hydroxyl-2,2,6,6-tetramethylpyridine, then the coupling graft reaction is performed to the acidified carbon nanotube and a prepolymerization polymer chain, and the polymer chain is grafted to the surface of the carbon nanotube to obtain a carbon nanotube grafted by the polymer. Since the surface of the carbon nanotube is wound with a great amount of polymer, the surface dangling bonds are increased, the dispersivity of the modified carbon nanotube in the medium is enhanced, the chain length of the polymer can be controlled through the mixture ratio of the active site and the monomer, and the invention canbe applied to various field of biological medicine, plastics, rubber, coating, and the like; and especially, the invention can utilize the performances of different polymers, greatly enhances the performance of the carbon nanotube, can select and manufacture the modified carbon nanotube with the characteristics according to the actual demands and further extends the application range of the carbon nanotube.
Description
Technical field
The present invention relates to the modification field of carbon nanotube, relate in particular to a kind of preparation method of modified carbon nano-tube.
Background technology
Since carbon nanotube in 1991 is found, carbon nanotube is just because of its particular structure and excellent extremely people's attention of performance, have performances such as high strength, high-heat performance and specific conductivity because of it, make it all receive higher concern aspect theoretical research field and the practical application.Why carbon nanotube has so many advantages, mainly is its π key conjugated structure, still, on the other hand, because the Van der Waals force that it causes interacts, causes the carbon nanotube ratio to be easier to reunite, thereby is difficult to be dissolved in the organic or inorganic solvent.This insoluble has seriously limited the Application Areas and the development prospect of carbon nanotube.Therefore, in order to improve the dissolving dispersive ability of carbon nanotube, create good interface, increase the interface binding power of itself and matrix, need carry out processing such as modification and finishing functionalization carbon nanotube.Up to the present, the method for functionalization mainly contains two kinds: non-covalent chemically modified and covalent chemical are modified, and that the method for functionalization is mainly utilized is organic and inorganic, biological chemistry and polymkeric substance wait and realize.
In the method for various covalent functionalization carbon nanotubes, it is a more attractive method that polymkeric substance is anchored on the carbon nanotube, because two materials with different properties can combine and obtain a kind of hybrid material.This can realize by grafting and implantation method.Preceding a kind of approach can be finished by the carboxylic group direct reaction of carbon nano tube surface after the acidifying, the line polymer that this method utilization end has functional group is easy to realize, but, the shortcoming of engrafting method is the steric hindrance of carbon nanotube, makes that the polymer chain of pre-grafting is lower at the grafting density of carbon nano tube surface.And implantation method relates to the in-situ polymerization of monomer from the initiation point of carbon nano tube surface, is easy to generate higher grafting density.Therefore, methods such as atom transfer radical polymerization, radical polymerization, anionoid polymerization, ring-opening metathesis polymerization, reversible addition-fragmentation chain transfer free radical polymerization have been used to the covalent functionalization carbon nanotube, yet, by implantation method, be difficult to obtain controlled molecular weight at the polymkeric substance of the surface grafting of carbon nanotube.This just need seek a kind of method of modifying that not only can high grafting density arranged but also can make the controlled carbon nanotube of the molecular weight of polymkeric substance in carbon nano tube surface, thereby expands the application space of carbon nanotube.
Summary of the invention
The present invention provides a kind of preparation method of modified carbon nano-tube for solving above-mentioned defective of the prior art, and the carbon nanotube science of carrying out is handled, and to improve the carbon nanotube performance, expands the application space of carbon nanotube.
For solving the problems of the technologies described above, the present invention program comprises:
A kind of preparation method of modified carbon nano-tube, described modified carbon nano tube tube preparation method may further comprise the steps:
A, produce the acidifying carbon nanotube, under ultrasonication, reflux treatment condition, 0.5-5 the original carbon nanotube of weight part is fully reaction in acid with strong oxidizing property, after will reacting back mixture process deionized water dilution, the processing of millipore filtration vacuum filtration, through repeatedly flushing, during to washing fluid to neutrality, the product complete drying under vacuum state with after the flushing obtains the acidifying carbon nanotube;
B, produce the carbon nanotube that the surface has nitroxyl free radical, with described acidifying carbon nanotube and 4-hydroxyl-2,2,6,6-tetramethyl pyridine nitroxyl free radical, 4-dimethylaminopyridine, N, N '-dicyclohexylcarbodiimide thorough mixing is in solvent, under the powerful agitation condition of 20 ℃-80 ℃ and magnetic force fully after the reaction, should react products therefrom through the millipore filtration vacuum filtration and after repeatedly washing, complete drying under 0 ℃-180 ℃ vacuum state obtains the carbon nanotube that the surface has nitroxyl free radical again;
C, produce the macromole evocating agent that end has halogen group, small molecules initiator with the 0.1-5 weight part, 0.1-5 the catalyzer of weight part, 0.1-5 the solvent of the ligand of weight part and 1-50 parts by volume is put into container and is sealed, in this container, charge into argon gas or nitrogen 1min-100min, to this container carry out three times freezing-vacuumize-thaw cycles after, the double bond monomer that contains that adds the 0.1-100 parts by volume in this container also seals, in this container, charge into argon gas or nitrogen 1min-100min, to this container carry out three times freezing-vacuumize-thaw cycles, under 0 ℃ of-150 ℃ of condition, fully react 0.1h-1000h then, after viscosity obviously increases in the container, stop this reaction, the crude product dissolution with solvents that this reaction is obtained, and after removing impurity such as colored transiting state metal ion by the neutral alumina pillar, the revaporization drying obtains the macromole evocating agent that end has halogen group;
D, the surface that obtains among the described step B is had-2,2,6, the carbon nanotube 0.1-10 weight part of 6-tetramethyl pyridine nitroxyl free radical, the end that obtains among the described step C has the macromole evocating agent 0.1-10 weight part of halogen group, ligand 0.1-5 weight part and solvent 1-100 parts by volume are put into container, with logical argon gas or nitrogen 1min-100min after the container sealing, and to this container carry out three times freezing-vacuumize-thaw cycles, fully reaction under 0 ℃ of-150 ℃ of condition, should react products therefrom with after the dissolution with solvents dilution, through millipore filtration vacuum filtration and repeatedly washing, complete drying under 0 ℃ of-180 ℃ of condition again obtains the carbon nanotube of polymer graft modification.
Described preparation method, wherein, described steps A is further comprising the steps of:
A1, the original carbon nanotube of 0.5-5 weight part is put into the acid with strong oxidizing property of 20-200 parts by volume, behind 0-100kHz ultrasonication 0.1h-100h, at 20 ℃ of-200 ℃ of reflux and abundant reaction 0.5h-100h;
A2, after reaction in the steps A 1 finishes, when treating that temperature is cooled to room temperature, post reaction mixture is diluted with deionized water, carry out centrifugation then and go out most of acid, with the solid dispersed that obtains in deionized water, and through the millipore filtration vacuum filtration, product behind the suction filtration is repeatedly washed, during to washing fluid to neutrality, the product complete drying under 0 ℃-180 ℃ vacuum state with after the flushing obtains the acidifying carbon nanotube.
Described preparation method, wherein, used original carbon nanotube is the single wall or the multi-walled carbon nano-tubes of arc-over, catalyse pyrolysis, laser evaporation method and template preparation in the described steps A.
Described preparation method, wherein, used acid with strong oxidizing property is the mixing acid of the vitriol oil, concentrated nitric acid, the vitriol oil and concentrated nitric acid or the mixing acid of the hydrogen peroxide and the vitriol oil in the described steps A.
Described preparation method, wherein, used solvent is dimethyl sulfoxide (DMSO), N among described step B, described step C and the described step D, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), methylene dichloride, ethylene dichloride, methyl alcohol, acetonitrile, propyl alcohol, ethanol, acetone, butanone, triethylamine, pyridine, dimethylamino pyridine, deionized water or toluene equal solvent, or by the mixture of above-mentioned solvent composition.
Described preparation method, wherein, the small molecules initiator is to contain on the α position to induce or the compound of conjugation group haloalkane among the described step C, it is small molecules initiators such as alpha-halo ethane, 2-bromine normal butane, α, the benzene sulfonyl chloride of α '-dibromo xylene, halogen ester, halo nitrile, para-orientation, alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride, alpha-chloro propionyl chloride.
Described preparation method, wherein, containing double bond monomer among the described step C is vinyl cyanide, vinylbenzene, methyl acrylate, methyl methacrylate, acrylamide, Methacrylamide, Dimethylaminoethyl Methacrylate, the N-N-isopropylacrylamide, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester, the methacrylic acid hydroxy butyl ester, vinylformic acid ammonia ethyl ester, aminoethyl methacrylate, p-chloromethyl styrene, between 1-chloro-4-methyl-benzene, N, the N-DMAA, N, N-dimethyl-aminoethyl methacrylate, N, N-dimethyl-Methacrylamide, N-isopropyl-methyl acrylamide, N, N-diethyl acrylamide, N, N-diethyl-4-methyl-acrylamide, N, N-dihydroxy ethyl acrylamide, N-hydroxyethyl acrylamide, the N-hydroxyethyl methacrylamide, N-methyl acrylamide, N-aminoethyl acrylamide, N-aminoethyl-Methacrylamide, N-(2-dimethylamino) ethyl acrylamide etc. contains double bond monomer.
Described preparation method, wherein, used catalyzer is the metallic compound that contains univalent copper ion, monovalence iron ion, pentavalent molybdenum ion, pentavalent rhenium ion, divalent ruthenium ion, monovalence nickel ion or divalence palladium ion among the described step C, such as metallic compounds such as cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ruthenous chloride, bromination naphthyl cyanide nickel, acid chlorides.
Described preparation method, wherein, used ligand is dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine among the described step C.
Described preparation method, wherein, used ligand is dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine among the described step D.
The invention provides a kind of preparation method of modified carbon nano-tube, introduce 2 in carbon nano tube surface, 2,6,6-tetramethyl pyridine nitroxyl free radical, cause the vinyl monomer controllable free-radical polymerisation by atom transfer radical polymerization method, and make above-mentioned two kinds of free radicals carry out coupling, the carbon nanotube that preparation has the controllable molecular weight polymer modification; The carbon nano tube surface of the present invention's preparation is wound with number of polymers, surperficial dangling bonds have been increased, improved its dispersiveness in medium, provide the basis for further modifying, and the chain length of polymkeric substance can be controlled by initiating activity point and monomeric proportioning, various functional groups can be changed by different monomers, have the hydrophilic polymers molecular chain, have fabulous dissolution dispersity, can in solution, adsorb, can be applied to fields such as biological medicine micropartical of different nature; And this carbon nanotube has good assimilation effect to microwave, can be applied in plastics, rubber, coating and the coating, also this carbon nanotube can be made film forming separately; Especially can utilize different polymer properties, further enlarge the application space of this carbon nanotube, such as utilizing this carbon nanotube making high-strength special type material or adding in the high-strength special type material.
Description of drawings
Fig. 1 is a nuclear magnetic spectrum of modifying the post-modification carbon nanotube among the present invention through polystyrene.
Embodiment
Below with reference to specific embodiment, the present invention is carried out comparatively detailed explanation.
The preparation method of a kind of modified carbon nano-tube provided by the invention, introduce nitroxyl free radical in carbon nano tube surface, cause the vinyl monomer controllable free-radical polymerisation by atom transfer radical polymerization method, and make above-mentioned two kinds of free radicals carry out coupling, improve the carbon nanotube performance, expanded the application space of carbon nanotube.The inventive method specifically may further comprise the steps:
A, the original multi-walled carbon nano-tubes of 0.5-5 weight part is put into the acid with strong oxidizing property of 20-200 parts by volume, behind 0-100kHz ultrasonication 0.1h-100h, at 20 ℃ of-200 ℃ of reflux and abundant reaction 0.5h-100h;
After B, above-mentioned reaction finish, when treating that temperature is cooled to room temperature, post reaction mixture is diluted with deionized water, carry out centrifugation then and remove most of acid, with the solid dispersed that obtains in deionized water, and through the millipore filtration vacuum filtration, product behind the suction filtration is repeatedly washed, during to washing fluid to neutrality, the product complete drying under 0 ℃-180 ℃ vacuum state with after the flushing obtains the acidifying carbon nanotube;
C, with described acidifying carbon nanotube and 4-hydroxyl-2,2,6,6-tetramethyl pyridine nitroxyl free radical, 4-dimethylaminopyridine, N, N '-dicyclohexylcarbodiimide thorough mixing are in organic solvent, under 20 ℃-80 ℃, after powerful magnetic agitation is fully reacted, should react products therefrom through the millipore filtration vacuum filtration and repeatedly the washing obtain clean product, with this clean product complete drying under 0 ℃-180 ℃ vacuum state, obtain the carbon nanotube that the surface has nitroxyl free radical then;
D, small molecules initiator with the 0.1-5 weight part, 0.1-5 the catalyzer of weight part, 0.1-5 the solvent of the ligand of weight part and 1-50 parts by volume is put into container and is sealed, in this container, charge into argon gas or nitrogen 1min-100min, to this container carry out three times freezing-vacuumize-thaw cycles after, the double bond monomer that contains that adds the 0.1-100 parts by volume in this container also seals, in this container, charge into argon gas or nitrogen 1min-100min, to this container carry out three times freezing-vacuumize-thaw cycles, under 0 ℃ of-150 ℃ of condition, fully react 0.1hr-1000hr then, after viscosity obviously increases in the container, stop this reaction, crude product dissolution with solvents with above-mentioned reaction, and remove impurity such as colored transiting state metal ion by the neutral alumina pillar, be spin-dried for solvent through Rotary Evaporators again, in vacuum-drying, obtain the macromole evocating agent that end has halogen group;
E, the carbon nanotube 0.1-10 weight part that the surface that obtains among the described step C is had nitroxyl free radical, the end that obtains among the described step D has the macromole evocating agent 0.1-10 weight part of halogen group, ligand 0.1-5 weight part and solvent 1-100 parts by volume are put into container, with container sealing backlash argon gas or nitrogen 1min-100min, and to this container carry out three times freezing-vacuumize-thaw cycles, fully reaction under 0 ℃ of-150 ℃ of condition, should react the gained crude product with after the dissolution with solvents dilution, through millipore filtration vacuum filtration and repeatedly washing, complete drying under 0 ℃ of-180 ℃ of condition again obtains the carbon nanotube of polymer graft modification.
In above-mentioned treating processes, used original carbon nanotube is the single wall or the multi-walled carbon nano-tubes of arc-over, catalyse pyrolysis, laser evaporation method and template preparation in the described steps A; Used acid with strong oxidizing property is the mixing acid of the vitriol oil, concentrated nitric acid, the vitriol oil and concentrated nitric acid or the mixing acid of the hydrogen peroxide and the vitriol oil.Used solvent is dimethyl sulfoxide (DMSO), N in described step C, described step D and the described step e, the mixed solvent that dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), methylene dichloride, ethylene dichloride, methyl alcohol, acetonitrile, propyl alcohol, ethanol, acetone, butanone, triethylamine, pyridine, dimethylamino pyridine, deionized water, toluene equal solvent or above-mentioned solvent merge mutually.The small molecules initiator is to contain on the α position to induce or the compound of conjugation group haloalkane among the described step D, it is initiators such as alpha-halo ethane, 2-bromine normal butane, α, the benzene sulfonyl chloride of α '-dibromo xylene, halogen ester, halo nitrile, para-orientation, alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride, alpha-chloro propionyl chloride; Containing double bond monomer is vinyl cyanide, vinylbenzene, methyl acrylate, methyl methacrylate, acrylamide, Methacrylamide, Dimethylaminoethyl Methacrylate, the N-N-isopropylacrylamide, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester, the methacrylic acid hydroxy butyl ester, vinylformic acid ammonia ethyl ester, aminoethyl methacrylate, p-chloromethyl styrene, between 1-chloro-4-methyl-benzene, N, the N-DMAA, N, N-dimethyl-aminoethyl methacrylate, N, N-dimethyl-Methacrylamide, N-isopropyl-methyl acrylamide, N, N-diethyl acrylamide, N, N-diethyl-4-methyl-acrylamide, N, N-dihydroxy ethyl acrylamide, N-hydroxyethyl acrylamide, the N-hydroxyethyl methacrylamide, N-methyl acrylamide, N-aminoethyl acrylamide, N-aminoethyl-Methacrylamide, N-(2-dimethylamino) ethyl acrylamide etc. contains double bond monomer; Used catalyzer is the metallic compound that contains univalent copper ion, monovalence iron ion, pentavalent molybdenum ion, pentavalent rhenium ion, divalent ruthenium ion, monovalence nickel ion or divalence palladium ion, for example cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ReO
2I (PPh
3)
2, RuCl
2, Ni (NCN) Br, etc. metallic compound.Used ligand is dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine in described step D and the step e.
The modified carbon nano-tube and the former carbon nanotube that adopt the inventive method to obtain compare as can be known: the multi-walled carbon nano-tubes before handling, and mutual mat, port closed, pipe range is longer, and is the shape that significantly curls, and is rough, also has impurity to exist; The outer part of open tube of the modified carbon nano-tube of handling through the inventive method has coated polymkeric substance, it is big that the diameter of pipe becomes, and in the process of the test reacted product is repeatedly cleaned with the methylene dichloride equal solvent, unreacted polymkeric substance is washed off, unreacted polymkeric substance does not have physics to be wrapped on the carbon nanotube, so under transmission electron microscope, the part of observed enveloped carbon nanometer tube is the polymer chain that is grafted on the carbon nanotube, because the existence of polymer chain, make carbon nano tube modified at methylene dichloride, good dissolution dispersity is arranged in tetrahydrofuran (THF) and the toluene, increase surperficial dangling bonds, improved the dispersiveness of modified carbon nano-tube in medium.
Embodiment one
With the multi-walled carbon nano-tubes is starting raw material, acidified, then with the multi-walled carbon nano-tubes after the acidifying, with 4-hydroxyl-2,2,6, behind the 6-tetramethyl pyridine nitroxyl free radical dehydration condensation, the polystyrene chain with pre-polymerization carries out the coupling graft reaction again, and polystyrene chain is grafted to carbon nano tube surface, obtain the carbon nanotube of copolymer grafted, effectively improved the dispersiveness of carbon nanotube in organic solvent.
A, multi-walled carbon nano-tubes 3g, nitric acid 40mL, sulfuric acid 120mL are joined 1000mL have in the flask of prolong, and carry out brute force and stir; Flask is immersed 10min makes its good distribution in the ultrasonic bath of 59KHz; To this flask oil bath heating, reaction 120min is increased to 120 ℃ with oil bath temperature by 90 ℃ simultaneously gradually then, and the persimmon gas of Chan Shenging utilizes plastic catheter to collect and handle with sodium hydroxide solution via prolong during this period; When treating that above-mentioned reaction finishes, with this flask cool to room temperature, then reaction mixture is diluted with deionized water, separate with whizzer again, pass through the polyvinylidene fluoride film vacuum filtration of 0.22 μ m then, and repeatedly wash, approach 7 until washing fluid pH value, at dry 24h under 50 ℃ of conditions of vacuum, obtain the acidifying carbon nanotube again;
B, in the 50mL ampoule, add acidifying carbon nanotube 0.9g, the 4-hydroxyl-2 of gained among the step a respectively, 2,6,6-tetramethyl pyridine nitroxyl free radical 0.432g, 4-dimethylamino pyridine 0.102g and N, N '-dicyclohexylcarbodiimide 0.519g, and make solvent with methylene dichloride, and under the magnetic agitation condition, room temperature reaction 24h; And the crude product of above-mentioned reaction gained diluted dissolving with methylene dichloride, then the reaction product after the dilution dissolving is carried out centrifugation, and collecting precipitation thing, should react products therefrom through the millipore filtration vacuum filtration and repeatedly washing obtain clean product, complete drying under 0 ℃-180 ℃ vacuum state obtains the carbon nanotube that the surface has nitroxyl free radical again;
C, in the ampoule of another 50mL, add 2 bromo-isopropylformic acid second fat 1.34mmol, cuprous bromide 0.192g, dipyridyl 0.209g and the 12ml vinylbenzene 104.88mmoL of 0.2ml respectively after, seal this ampoule, and this ampoule is carried out three cyclical operations of liquid nitrogen freezing-vacuumize-thaw; Then this ampoule is placed 90 ℃ oil bath, and under the magnetic agitation condition, fully react; After question response is finished, the crude product that obtains is dissolved with methylene dichloride, and remove impurity such as colored transiting state metal ion by the neutral alumina pillar, and in methyl alcohol, precipitate, it is carried out vacuum filtration, dry 24h obtains white product under vacuum condition again, and the macromole evocating agent that end has halogen group is the polystyrene bromine;
D, in second 50mL ampoule, add the surface that obtains among the step b respectively and have the carbon nanotube 0.126mmol of nitroxyl free radical, macromole evocating agent polystyrene bromine 0.126mmol that obtains among the step c and 0.053ml PMDETA 0.252mmol, and with 5ml toluene as solvent, seal this ampoule, and this ampoule carried out three cyclical operations of liquid nitrogen freezing-vacuumize-thaw, then this ampoule is placed 90 ℃ oil bath, fully react 24h under the magnetic agitation condition, after question response finishes, the crude product that obtains is dissolved with methylene dichloride, and pass through filtering with microporous membrane, then products therefrom is washed repeatedly, with the product dry 24h under vacuum condition after the flushing, obtain the modified carbon nano-tube after polystyrene is modified.As shown in Figure 1, the nuclear magnetic spectrogram of comparing with the polystyrene bromine after polystyrene and the multi-walled carbon nano-tubes coupling, near 4.4-4.5ppm the proton peak corresponding to the methylene radical of-CH (Ph)-Br has disappeared, and the vibration peak of the vibration peak of phenyl ring and methyne on the main chain and methylene radical occurs near 6.45-7.25ppm and 3.48-3.64ppm respectively, and this just means that also coupled reaction is successful.Through foregoing description as can be known, reaction of the present invention is fully, is successful, and the various performances of modified carbon nano-tube after modifying through polystyrene have obtained significantly improving, and have expanded the application space of carbon nanotube.
Embodiment two
With the multi-walled carbon nano-tubes is starting raw material, acidified, then with the multi-walled carbon nano-tubes after the acidifying (MWNT-COOH), with 4-hydroxyl-2,2,6, behind the 6-tetramethyl pyridine nitroxyl free radical dehydration condensation, the polyacrylonitrile chain with pre-polymerization carries out the coupling graft reaction again, and the polyacrylonitrile chain is grafted to carbon nano tube surface, obtain the carbon nanotube of polymer graft, effectively improved the dispersiveness of carbon nanotube in organic solvent.
A, multi-walled carbon nano-tubes 3g, nitric acid 40mL, sulfuric acid 120mL are joined 1000mL have in the flask of prolong, and carry out brute force and stir; Flask is immersed 10min makes its good distribution in the ultrasonic bath of 59KHz; To this flask oil bath heating, reaction 120min is increased to 120 ℃ with oil bath temperature by 90 ℃ simultaneously gradually then, and the persimmon gas of Chan Shenging utilizes plastic catheter to collect and handle with sodium hydroxide solution via prolong during this period; When treating that above-mentioned reaction finishes, with this flask cool to room temperature, then reaction mixture is diluted with deionized water, separate with whizzer again, pass through the polyvinylidene fluoride film vacuum filtration of 0.22 μ m then, and the reaction product after filtering is repeatedly washed, approach 7 until washing fluid pH value, dry 24h under 50 ℃ of conditions of vacuum obtains the acidifying carbon nanotube again;
B, in the 50mL ampoule, add acidifying carbon nanotube 0.9g, the 4-hydroxyl-2 of gained among the step a respectively, 2,6,6-tetramethyl pyridine nitroxyl free radical 0.432g, 4-dimethylamino pyridine 0.102g and N, N '-dicyclohexylcarbodiimide 0.519g, and make solvent with methylene dichloride, and under the magnetic agitation condition, room temperature reaction 24h; And the crude product of above-mentioned reaction gained diluted dissolving with methylene dichloride, then the reaction product after the dilution dissolving is carried out centrifugation, and collecting precipitation thing, should react products therefrom through the millipore filtration vacuum filtration and repeatedly washing obtain clean product, complete drying under 0 ℃-180 ℃ vacuum state obtains the carbon nanotube that the surface has nitroxyl free radical again;
C, in another 50mL ampoule, add 2 bromo-isopropylformic acid second fat 1.34mmol, cuprous bromide 0.192g, dipyridyl 0.209g, 4.4ml vinyl cyanide 67mmol and the 3.0mlN of 0.2ml respectively, dinethylformamide, seal this ampoule, and this ampoule is carried out three cyclical operations of liquid nitrogen freezing-vacuumize-thaw; Then this ampoule is placed 50 ℃ oil bath, and under the magnetic agitation condition, fully react 12h; After question response is finished, to the crude product N that obtains, the dinethylformamide dissolving, and remove impurity such as colored bivalent cupric ion by the neutral alumina pillar, crude product after will handling then precipitates in ether, dissolve then-precipitation operation obtains the buff powder product for twice, and with this buff powder product dry 12h under 40 ℃ of vacuum conditions, obtaining the macromole evocating agent that end has halogen group is the polyacrylonitrile bromine;
D, in second 50mL ampoule, add the surface that obtains among the step b respectively and have the carbon nanotube 0.126mmol of nitroxyl free radical, macromole evocating agent polyacrylonitrile bromine 0.126mmol that obtains among the step c and 0.053ml PMDETA 0.252mmol, and use 5mlN, dinethylformamide is as solvent, seal this ampoule, and this ampoule carried out three cyclical operations of liquid nitrogen freezing-vacuumize-thaw, then this ampoule is placed 80 ℃ oil bath, fully react 24h under the magnetic agitation condition, after question response finishes, with the crude product N that obtains, the dinethylformamide dissolving, and by the tetrafluoroethylene filtering with microporous membrane, then products therefrom is washed repeatedly, dry 24h under 40 ℃ of vacuum conditions obtains the modified carbon nano-tube after polyacrylonitrile is modified again.Through foregoing description as can be known, the modified carbon nano-tube after polyacrylonitrile is modified that obtains by above-mentioned reaction, the various performances of modified carbon nano-tube after this process polyacrylonitrile is modified have obtained significantly improving, and have effectively improved the dispersiveness of carbon nanotube in organic solvent.
The preparation method of a kind of modified carbon nano-tube provided by the invention, with the carbon nanotube after the acidifying, with 4-hydroxyl-2,2,6, after 6-tetramethyl pyridine nitroxyl free radical is carried out dehydration condensation, polymer chain with pre-polymerization carries out the coupling graft reaction again, polymer chain is grafted to carbon nano tube surface, obtained the carbon nanotube of polymer graft, be wound with number of polymers in carbon nano tube surface, increased surperficial dangling bonds, improved the dispersiveness of modified carbon nano-tube in medium, provide the basis for further modifying, and the chain length of polymkeric substance can be controlled by initiating activity point and monomeric proportioning, and various functional groups can be changed by different monomers, have the hydrophilic polymers molecular chain, has fabulous dissolution dispersity, can be applied to biological medicine, plastics, rubber, coating, fields such as coating also can make film forming separately with this carbon nanotube, also this carbon nanotube can be made as the high-strength special type material or add in the high-strength special type material; Especially can utilize different polymer properties, increase substantially the carbon nanotube performance, and can select to make the modified carbon nano-tube that possesses certain specific character as required, further expand the application space of this carbon nanotube; The foregoing description only is for example, and non exhaustive, can the method according to this invention principle carry out various distortion, all should fall into protection scope of the present invention.
Should be understood that; above-mentioned description at preferred embodiment is comparatively detailed; can not therefore think restriction to scope of patent protection of the present invention; those of ordinary skill in the art is under enlightenment of the present invention; do not breaking away under the scope situation that claim of the present invention protects; can also make various deformation such as replacement, simple combination, these all fall within protection scope of the present invention, and the scope of asking for protection of the present invention should be as the criterion with claims.
Claims (4)
1. the preparation method of a modified carbon nano-tube, described modified carbon nano tube tube preparation method may further comprise the steps:
A, produce the acidifying carbon nanotube, under ultrasonication, reflux treatment condition, 0.5-5 the original carbon nanotube of weight part is fully reaction in acid with strong oxidizing property, after will reacting back mixture process deionized water dilution, the processing of millipore filtration vacuum filtration, again through repeatedly flushing, during to washing fluid to neutrality, the product complete drying under vacuum state with after the flushing obtains the acidifying carbon nanotube;
B, produce the surface and have 4-hydroxyl-2,2,6, the carbon nanotube of 6-tetramethyl pyridine nitroxyl free radical, with described acidifying carbon nanotube and 4-hydroxyl-2,2,6,6-tetramethyl pyridine nitroxyl free radical, 4-dimethylaminopyridine, N, N '-dicyclohexylcarbodiimide thorough mixing under the powerful agitation condition of 20 ℃-80 ℃ and magnetic force fully after the reaction, should react products therefrom after the millipore filtration vacuum filtration also repeatedly washs in solvent, complete drying under 0 ℃-180 ℃ vacuum state obtains the carbon nanotube that the surface has nitroxyl free radical again;
C, produce the macromole evocating agent that end has halogen group, small molecules initiator with the 0.1-5 weight part, 0.1-5 the catalyzer of weight part, 0.1-5 the solvent of the ligand of weight part and 1-50 parts by volume is put into container and is sealed, in this container, charge into argon gas or nitrogen 1min-100min, to this container carry out three times freezing-vacuumize-thaw cycles after, the double bond monomer that contains that adds the 0.1-100 parts by volume in this container also seals, in this container, charge into argon gas or nitrogen 1min-100min, to this container carry out three times freezing-vacuumize-thaw cycles, under 0 ℃ of-150 ℃ of condition, fully react 0.1h-1000h then, after viscosity obviously increases in the container, stop this reaction, the crude product dissolution with solvents that this reaction is obtained, and after removing impurity such as colored transiting state metal ion by the neutral alumina pillar, the revaporization drying obtains the macromole evocating agent that end has halogen group; D, the carbon nanotube 0.1-10 weight part that the surface that obtains among the described step B is had nitroxyl free radical, the end that obtains among the described step C has the macromole evocating agent 0.1-10 weight part of halogen group, ligand 0.1-5 weight part and solvent 1-100 parts by volume are put into container, with logical argon gas or nitrogen 1min-100min after the container sealing, and to this container carry out three times freezing-vacuumize-thaw cycles, fully reaction under 0 ℃ of-150 ℃ of condition, should react products therefrom with after the dissolution with solvents dilution, through millipore filtration vacuum filtration and repeatedly washing, complete drying under 0 ℃ of-180 ℃ of condition again obtains the carbon nanotube of polymer graft modification;
Wherein, used solvent is dimethyl sulfoxide (DMSO), N among described step B, described step C and the described step D, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), methylene dichloride, ethylene dichloride, methyl alcohol, acetonitrile, propyl alcohol, ethanol, acetone, butanone, triethylamine, pyridine, dimethylamino pyridine, deionized water or toluene, or by the mixture of above-mentioned solvent composition;
The small molecules initiator is to contain on the α position to induce or the compound of conjugation group haloalkane among the described step C, it is alpha-halo ethane, 2-bromine normal butane, α, the benzene sulfonyl chloride of α '-dibromo xylene, halogen ester, halo nitrile, para-orientation, alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride or alpha-chloro propionyl chloride;
Containing double bond monomer among the described step C is vinyl cyanide, vinylbenzene, methyl acrylate, methyl methacrylate, acrylamide, Methacrylamide, Dimethylaminoethyl Methacrylate, the N-N-isopropylacrylamide, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, the vinylformic acid hydroxy butyl ester, the methacrylic acid hydroxy butyl ester, vinylformic acid ammonia ethyl ester, aminoethyl methacrylate, p-chloromethyl styrene, between 1-chloro-4-methyl-benzene, N, the N-DMAA, N, N-dimethyl-aminoethyl methacrylate, N, N-dimethyl-Methacrylamide, N-isopropyl-methyl acrylamide, N, N-diethyl acrylamide, N, N-diethyl-4-methyl-acrylamide, N, N-dihydroxy ethyl acrylamide, N-hydroxyethyl acrylamide, the N-hydroxyethyl methacrylamide, N-methyl acrylamide, N-aminoethyl acrylamide, N-aminoethyl-Methacrylamide, N-(2-dimethylamino) ethyl acrylamide;
Used ligand is dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine among the described step C;
Used ligand is dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine among the described step D;
Used catalyzer is cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ruthenous chloride, bromination naphthyl cyanide nickel, acid chloride among the described step C.
2. preparation method according to claim 1 is characterized in that: described steps A is further comprising the steps of:
A1, the original carbon nanotube of 0.5-5 weight part is put into the acid with strong oxidizing property of 20-200 parts by volume, behind 0-100kHz ultrasonication 0.1h-100h, at 20 ℃ of-200 ℃ of reflux and abundant reaction 0.5h-100h;
A2, after reaction in the steps A 1 finishes, when treating that temperature is cooled to room temperature, post reaction mixture is diluted with deionized water, carry out centrifugation then and remove most of acid, with the solid dispersed that obtains in deionized water, and through the millipore filtration vacuum filtration, product behind the suction filtration is repeatedly washed, during to washing fluid to neutrality, the product complete drying under 0 ℃-180 ℃ vacuum state with after the flushing obtains the acidifying carbon nanotube.
3. preparation method according to claim 1 and 2 is characterized in that: used original carbon nanotube is the single wall or the multi-walled carbon nano-tubes of arc-over, catalyse pyrolysis, laser evaporation method and template preparation in the described steps A.
4. preparation method according to claim 3 is characterized in that: used acid with strong oxidizing property is the mixing acid of the vitriol oil, concentrated nitric acid, the vitriol oil and concentrated nitric acid or the mixing acid of the hydrogen peroxide and the vitriol oil in the described steps A.
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| CN102516540B (en) * | 2011-12-20 | 2013-10-23 | 哈尔滨工业大学 | Method for grafting SWNT (single-walled carbon nanotube) into modified PIPD (poly[2,5-dihydroxy-1,4-phenylenepyridinodiimidazole]) |
| CN104558629B (en) * | 2013-10-17 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of method of microwave radiation to carbon nanotube graft modification |
| CN103923252B (en) * | 2014-04-21 | 2017-01-11 | 中国科学技术大学 | Thermoplastic elastomer and preparation method thereof |
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| CN113753879A (en) * | 2020-06-05 | 2021-12-07 | 重庆科技学院 | Temperature-sensitive polymer modified carbon nanotube composite material and preparation method thereof |
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