CN101092739A - Method for preparing high water soluble Nano carbon tube grafted by super branched polymer - Google Patents
Method for preparing high water soluble Nano carbon tube grafted by super branched polymer Download PDFInfo
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Abstract
This invention discloses a method for preparing highly water-soluble carbon nanotubes by grafting modification with hyper branched polymer. The method comprises: purifying carbon nanotubes with a highly oxidative acid to form active groups at the sidewalls and the ends, modifying with polyamine or polyol to form initiating groups at the surfaces, and then reacting between hyper branched polymer and the initiating groups for grafting to form large quantities of carboxyl or amine groups at the surfaces of carbon nanotubes so that carbon nanotubes have high solubility and dispersibility in aqueous solvents. The obtained highly water-soluble carbon nanotubes have improved processability, and can be used in composite materials, hydrogen storage materials, electronics, sensors and biomaterials.
Description
Technical field
The present invention relates to carbon nanotube of a kind of surface modification and preparation method thereof, particularly utilize superelevation water-soluble carbon nanometer tube of grafted by super branched polymer and preparation method thereof, belong to field of nanometer material technology.
Background technology
Along with the mankind will become the understanding of the dominant technology of 21 century to nanosecond science and technology, people more and more press for and grasp and utilize nanoscale science and technology, thereby realize society, economic, scientific and technical comprehensive great-leap-forward development.Wherein, the discovery of carbon nanotube is a milestone on the World History.Over past ten years, carbon nanotube is the focus of World Science research always, because its distinctive immanent structure (length-to-diameter ratio, chirality etc.) and the peculiar physical properties (optics, electrical properties etc.) that shows, it has important application prospects in a lot of fields as a kind of new one-dimensional nano material, is 21 century one of the most promising nano material.
Yet, because carbon nanotube has huge molecular weight, insolubility (that is the bad dispersibility that has directly caused carbon nanotube, easily reunite), make carbon nanotube can not be as C60 the easy organic chemical reactions that carries out, this has seriously hindered the development of carbon nanotube chemical and the application of carbon nano-tube/polymer composite material.Therefore, necessaryly carbon nanotube is carried out organic chemistry modify, it can well be disperseed in media such as solvent, polymkeric substance, thereby bring into play the nano effect of carbon nanotube well.Wherein, water-soluble carbon nanometer tube is because its significant role in biotechnology (as microbiosensor etc.), and carbon nanotube solution of solubility problem in water is very urgent.
The acid treatment that people such as Richard E Smalley scrutinized carbon nanotube in 1998, obtained the products distribution situation under the different treatment condition, this has laid good basis (Science, 1998,280 (22): 1253-1255) for further studying later on.Afterwards, people's success such as Masahito Sano is grafted to the tenth generation branch-shape polymer PAMAM (poly (amidoamine)) carbon nano tube surface (Angew.Chem..2001,113 (24): 4797-4799).People such as Ya-Ping Sun have successively realized grafting (Nano Lett, 2001,1 (8), the 439-441 of some dendrimers; Chem.Mater.2001,13 (9): 2864-2869; J.Phys.Chem.B 2002,106 (6), 1294-1298).
The further research and the actual application prospect of carbon nanotube expanded in the development of carbon nano tube modified method to a certain extent, but from present present Research, carbon nano tube chemical decoration still is in the starting stage, awaits further developing with perfect.For example, content of carbon nanotubes is less relatively during the superpolymer grafted modified carbon nano tube, and the gained material can not embody the carbon nanotube characteristic; The terminal active group of high molecular polymer that is modified at carbon nano tube surface is less, and the products therefrom dissolving properties is very poor etc.
Summary of the invention
The objective of the invention is by chemical modification method, will contain grafted by super branched polymer that a large amount of active groups have excellent dissolution performance and dispersing property on carbon nanotube tube wall and port, thereby give the carbon nanotube high water soluble.
Content of the present invention is to be raw material with carbon nanotube, polyamine or polyvalent alcohol and hyperbranched polymer, modifies polyamine or polyvalent alcohol at the tube wall and the port of carbon nanotube earlier by molecular designing, utilizes grafted by super branched polymer carbon nano-tube modified afterwards.The carbon nano tube surface active group of grafted by super branched polymer and solubility property can be regulated by the kind and the molecular weight of hyperbranched polymer raw material, can prepare the carbon nanotube with good solubility property and dispersing property thus.
The preparation method of grafted by super branched polymer carbon nanotube of the present invention is as follows:
Step (a): place flask in container A 1 part of exsiccant carbon nanometer tube material of adding and 5～50 parts of acid with strong oxidizing property by weight, stir down and back flow reaction 0.5～100hr at 0～100 ℃, afterwards in 0～50 ℃ under the acid with strong oxidizing property effect with 0～100kHz ultrasonication, 0～50hr, with the filter membrane suction filtration, repetitive scrubbing is repeatedly to neutral, obtains the carbon nanotube behind the purifying behind 0～180 ℃ of following vacuum-drying 10～30hr;
Step (b): in container B, add 1 part and 5～50 parts polyamines of step (a) gained purifying carbon nano-tube or polyvalent alcohol by weight, mixed dissolution is in organic solvent, behind 0～100kHz ultrasonication, 10～100min, stir down and back flow reaction 0.5～100hr at 0～100 ℃, with the filter membrane suction filtration, repetitive scrubbing, 0～180 ℃ of following vacuum-drying obtains the carbon nanotube that the surface has hydroxyl or amido;
Step (c): in container C, add carbon nanotube that step (b) gained surface has hydroxyl or an amido by weight and be 1 part and contain 1～50 part of the hyperbranched polymer of the amino or end carboxyl of end, mixed dissolution is in organic solvent, behind 0～100kHz ultrasonication, 10～100min, stir down and back flow reaction 0.5～100hr at 0～150 ℃, with the filter membrane suction filtration, repetitive scrubbing, 0～180 ℃ of following vacuum-drying obtains the carbon nanotube of grafted by super branched polymer.
Used carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template, chemical Vapor deposition process preparation in the inventive method step (a).
Used acid with strong oxidizing property comprises 40～70% nitric acid, 40～100% sulfuric acid, 1/100～100/1 molar ratio, 40～100% nitric acid/sulfuric acid mixing acid, 1/100～100/1 molar ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio H in the inventive method step (a)
2O
2With sulfuric acid mixed solution, 1/100～100/1 mole of H
2O
2And sulfuric acid mixed solution.
Used polyamine or polyvalent alcohol material comprise ethylene glycol, quadrol, glycerol, third triamine, 1 in the inventive method step (b), 2-propylene glycol, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, diethanolamine, trolamine, N methyldiethanol amine, dimethylethanolamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol, polyethyene diamine.
Used hyperbranched polymer is to contain end carboxyl or amino hyper-branched polyester, polymeric amide, urethane, polyureas-ammonia ester, polysulfones amine, the polyesteramine of end in the inventive method step (c).
Solvent for use is dimethyl sulfoxide (DMSO), N among the inventive method step (b), (c), dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or contain the mixture of these solvents.
The inventive method has salient feature: the purification process of (1) carbon nanotube has and simple effectively utilizes the processing to carbon nanotube under differing temps of acid with strong oxidizing property and ultrasonic wave, makes carbon nanotube obtain purifying and possesses certain active group; (2) modifying method of carbon nanotube is easier behind the purifying, handle without chloride, and directly utilize its surface active groups to modify, and because a large amount of active groups that carbon nano tube surface occurs behind the purifying, thereby the efficient height of the finishing of assurance carbon nanotube; (3) carbon nanotube is modified easy and simple to handle with the grafting hyperbranched polymer, need not be as the protection of inert gas that needs in other hyperbranched polymer vegetation process, directly reflux operation gets final product under the certain temperature; (5) the hyperbranched polymer algebraically on grafting carbon nanotube surface is not high, on the basis of character such as destroying carbon nanometer tube height length-to-diameter ratio and electrovalence band structure not, has given carbon nanotube high water-soluble.
The high water soluble Nano carbon tube that utilizes the inventive method to obtain can detect by certain detection means, as adopting ultimate analysis, XPS or nuclear magnetic resonance method etc.
The inventive method utilizes the hyperbranched polymer of less algebraically carbon nano-tube modified, thereby guaranteed the relative content height of carbon nanotube in the products therefrom, and the hyperbranched polymer self character has guaranteed that the product surface possesses a large amount of terminal active groups, thereby realizes the water-soluble of carbon nanotube height.
Preparation method provided by the invention is simple, has the characteristics of controllability and quantification; The carbon nanotube of the surperficial tool grafting hyperbranched polymer of gained, in aqueous solvent, show outstanding dispersiveness, improved the workability of carbon nanotube greatly, for carbon nanotube has been paved road in the application in fields such as matrix material, hydrogen storage, electron device, transmitter, biomaterial.
Description of drawings
The XPS collection of illustrative plates of Fig. 1: embodiment 1
Embodiment
Embodiment 1:
Multiple-wall carbon nanotube with the catalytic pyrolysis method preparation is an initial raw material, utilizes acid with strong oxidizing property that carbon nanotube is carried out purification process, removes impurities in raw materials, simultaneously carbon nanotube is lacked the effect of cutting.Utilize the short active group of back carbon nano tube surface appearance and the effect of polyamine, the certain super cladodification initiating group on carbon nano tube surface is modified cut.Obtain hyperbranched poly (amide-ester) grafted carbon nanotube afterwards with by inclined to one side benzoic anhydride (benzene-1,2,4-tricarboxylic acid-1,2 acid anhydride) and diethanolamine synthetic hyperbranched poly (amide-ester) (hyperbranched polymer algebraically was five generations) reaction.
Step (a): put into 2g exsiccant multi-walled carbon nano-tubes and 40mL60% concentrated nitric acid in the 100mL flask that is placed with magnetic stick, 24h refluxes under 80 ℃ of magnetic agitation; Backflow discards supernatant liquid after finishing, and then pours the mixing acid that the 40mL volume ratio is 3/1 (98% sulfuric acid/60% nitric acid), supersound process 3hr under normal temperature in lower floor's black solid into.Discard supernatant liquid after the ultrasonic end, the lower black solid is mixed with suspension with the deionized water that contains 0.5% (volume ratio) Triton X-100 tensio-active agent.With vinylidene fluoride (PVDF) filter membrane (diameter 50mm, aperture 0.45um) and this suspension of film filter vacuum filtration, leach thing on the collection membrane.Repeating above-mentioned filtration procedure, is neutral until deionized water, and 60 ℃ of vacuum-drying 6hr promptly get the multi-walled carbon nano-tubes 1.92g of purifying.
Step (b): in the 100mL flask that is placed with magnetic stick, put into the carbon nanotube and the 0.7g diethanolamine (DEA) that get behind 1.5g step (a) the gained purifying, be mixed in 40mL solvent N, ultrasonication 30min in the dinethylformamide (DMF) makes it thorough mixing.110 ℃ of back flow reaction 24hr of mixed system.After reaction is finished,,, leach 60 ℃ of vacuum-drying 6hr of thing, obtained the carbon nanotube 1.45g through the diethanolamine modification of black with 0.45 μ m filtering with microporous membrane with unreacted diethanolamine of the ultrasonic flush away of deionized water (DEA) and unnecessary solvent.
Step (c): in the 50mL flask that is placed with magnetic stick, put into the carbon nanotube that 1.3g step (b) gained diethanolamine is modified, add 20mL 10% again by inclined to one side benzoic anhydride (benzene-1,2,4-tricarboxylic acid-1,2 acid anhydrides) and the DMF solution of diethanolamine synthetic hyperbranched poly (amide-ester) (hyperbranched polymer algebraically was five generations), ultrasonication 20min makes it thorough mixing, 100 ℃ of back flow reaction 48hr of mixed system.After reaction is finished,,, leach 60 ℃ of vacuum-drying 12hr of thing, obtained the carbon nanotube of the grafting and modifying hyperbranched poly (amide-ester) of black with 0.45 μ m filtering with microporous membrane with unreacted hyperbranched polymer of the ultrasonic flush away of deionized water and unnecessary solvent.
The N element (6%) that do not have in the original carbon nanotube of certain content appears in the gained result product when ultimate analysis, and the O constituent content is greatly improved after reaction (0.62% becomes 12%), in conjunction with XPS analysis, the peak of unexistent amide group of original carbon nanotube and carboxyl appears in the surface of the carbon nanotube after the modification, this explanation hyperbranched polymer in modification has been grafted to the surface of carbon nanotube really, and has introduced a large amount of water miscible active groups.Original carbon nanotube is dispersive not in water, and the dispersing property of products therefrom in aqueous solvent very outstanding (15mg/mL).
Embodiment 2:
On the basis of embodiment 1, step (a) is with embodiment 1, the diethanolamine input amount changes 1.4g in the step (b), 10% inclined to one side benzoic anhydride (benzene-1 in the step (c), 2,4-tricarboxylic acid-1,2 acid anhydride) and the DMF solution input amount of diethanolamine synthetic hyperbranched poly (amide-ester) (hyperbranched polymer algebraically was five generations) change 40mL into, other conditions are constant, obtained the carbon nanotube of the grafting and modifying hyperbranched poly (amide-ester) of black powder shape.
The gained result product compares with the embodiment products therefrom that N element (8.1%) and O element (0.62% becomes 14%) content change more obvious in the ultimate analysis, peakedness ratio embodiment 1 collection of illustrative plates of amide group and carboxyl is bigger among the XPS analysis result, the result is more clear obviously, modifies the dispersing property of after product in water improve (20mg/mL)
Embodiment 3:
On the basis of embodiment 1, step (a) is with embodiment 1, the diethanolamine input amount changes 2.1g in the step (b), 10% inclined to one side benzoic anhydride (benzene-1 in the step (c), 2,4-tricarboxylic acid-1,2 acid anhydride) and the DMF solution input amount of diethanolamine synthetic hyperbranched poly (amide-ester) (hyperbranched polymer algebraically was five generations) change 50mL into, other conditions are constant, obtained the carbon nanotube of the grafting and modifying hyperbranched poly (amide-ester) of black powder shape.
Gained result product N element (9.7%) and the relative embodiment 2 product results of O element (0.62% becomes 14.3%) content in ultimate analysis have certain change, the relative embodiment collection of illustrative plates of the peak value of amide group and carboxyl also has bigger increase among the XPS analysis result, the result further proves the grafting effect of amido and hyperbranched polymer, modifies the dispersing property of after product in water also very good (21mg/mL)
Embodiment 4:
On the basis of embodiment 1, unified the using of oxidizing acid is that volume ratio is the mixing acid of 3/1 (98% sulfuric acid/60% nitric acid) in the step (a), the magnetic agitation reflow treatment time is adjusted into 10hr, other conditions are constant, step (b), step (c) are consistent with embodiment 1, have obtained the carbon nanotube of the grafting and modifying hyperbranched poly (amide-ester) of black powder shape.
Gained result product N element (6.2%) and O element (0.62% becomes 11.7%) content in ultimate analysis is almost consistent with embodiment 1 product result, the position that occurs amide group and carboxyl among the XPS analysis result is also identical with peak value, the result proves the success of the grafting effect of amido and hyperbranched polymer equally, modifies the dispersing property of after product in water also very good (18mg/mL)
Embodiment 5:
On the basis of embodiment 1, oxidizing acid is unified with being 60% nitric acid in the step (a)) mixing acid, other conditions are constant.Step (b), step (c) are consistent with embodiment 1, have obtained the carbon nanotube of the grafting and modifying hyperbranched poly (amide-ester) of black powder shape.
Gained result product N element (5.5%) and O element (0.62% becomes 10.5%) content in ultimate analysis are compared with embodiment 1 product result to some extent and are reduced, but still can find out the obvious increase of two kinds of constituent contents, it is identical that XPS analysis result and embodiment 1 collection of illustrative plates are compared the position that amide group and carboxyl occur, peak value weakens to some extent, but the result proves the grafting effect of amido and hyperbranched polymer equally, modifies the good dispersion property (13mg/mL) of after product in water
Embodiment 6:
On the basis of embodiment 1, step (a) is with embodiment 1, and temperature of reaction becomes 130 ℃ in the step (b), and other conditions are constant, and step (c) has obtained the carbon nanotube of the grafting and modifying hyperbranched poly (amide-ester) of black powder shape with embodiment 1.
Gained result product N element (7.1%) and O element (0.62% becomes 12.4%) content in ultimate analysis are compared more obvious with embodiment 1, the peak value of amide group and carboxyl also increases to some extent among the XPS analysis result, the result has proved the grafting effect of amido and hyperbranched polymer, modifies the dispersing property of after product in water also very good (19mg/mL).
Claims (6)
1, a kind of method for preparing high water soluble Nano carbon tube of grafted by super branched polymer is characterized in that, may further comprise the steps:
Step (a): add 1 part of exsiccant carbon nanometer tube material by weight and 5～50 parts of acid with strong oxidizing property place reaction vessel A, stir down and back flow reaction 1～100hr at 0～100 ℃, afterwards in 0～50 ℃ under the acid with strong oxidizing property effect with 0～100kHz ultrasonication, 0.5～50hr, with the filter membrane suction filtration, repetitive scrubbing is repeatedly to neutral, obtains the carbon nanotube behind the purifying behind 0～180 ℃ of following vacuum-drying 10～30hr;
Step (b): in container B, add 1 part and 5～50 parts polyamines of step (a) gained purifying carbon nano-tube or polyvalent alcohol by weight, mixed dissolution is in organic solvent, behind 0～100kHz ultrasonication, 10～100min, stir down and back flow reaction 0.5～100hr at 0～100 ℃, with the filter membrane suction filtration, repetitive scrubbing, 0～180 ℃ of following vacuum-drying obtains the carbon nanotube that the surface has hydroxyl or amido;
Step (c): in container C, add carbon nanotube that step (b) gained surface has hydroxyl or an amido by weight and be 1 part and contain 1～50 part of the hyperbranched polymer of the amino or end carboxyl of end, mixed dissolution is in organic solvent, behind 0～100kHz ultrasonication, 10～100min, stir down and back flow reaction 0.5～100hr at 0～150 ℃, with the filter membrane suction filtration, repetitive scrubbing, 0～180 ℃ of following vacuum-drying obtains the carbon nanotube of grafted by super branched polymer.
2, preparation method according to claim 1 is characterized in that, used carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template, chemical Vapor deposition process preparation in the step (a).
3, preparation method according to claim 1, it is characterized in that used acid with strong oxidizing property comprises 40～70% nitric acid, 40～100% sulfuric acid, 1/100～100/1 molar ratio, 40～100% nitric acid/sulfuric acid mixing acid, 1/100～100/1 molar ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio H in the step (a)
2O
2With sulfuric acid mixed solution, 1/100～100/1 mole of H
2O
2And sulfuric acid mixed solution.
4, preparation method according to claim 1, it is characterized in that, used polyamine or polyvalent alcohol material comprise ethylene glycol, quadrol, glycerol, third triamine, 1 in the step (b), 2-propylene glycol, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, diethanolamine, trolamine, N methyldiethanol amine, dimethylethanolamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol, polyethyene diamine.
5, preparation method according to claim 1 is characterized in that, used hyperbranched polymer is to contain end carboxyl or amino hyper-branched polyester, polymeric amide, urethane, polyureas-ammonia ester, polysulfones amine, the polyesteramine of end in the step (c).
6, preparation method according to claim 1, it is characterized in that, step (b) is dimethyl sulfoxide (DMSO), N with the middle solvent for use of step (c), dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate, acetone, butanone, acetonitrile, propyl alcohol, ethanol, methyl alcohol or contain the mixture of these solvents.
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