CN1257944C - Core-shell type lipophilic-hydrophilic carbon nanometer tube and its preparation method - Google Patents
Core-shell type lipophilic-hydrophilic carbon nanometer tube and its preparation method Download PDFInfo
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Abstract
The present invention provides a core-shell type lipophilic-hydrophilic carbon nano tube and a preparation method thereof. After the carbon nano tube is treated, the surface of the carbon nano tube is provided with hydroxy or amino, and the product is retreated to obtain specific initiating radical groups. Then, atom transfer radical polymerization reaction is implemented to initiate the polymerization of lipophilicity monomers containing double bonds to obtain a single-stage lipophilicity macromolecule grafted carbon nano tube. Atom transfer radical polymerization reaction is implemented to continuously initiate the polymerization of (methyl) butyl acrylate monomers, and then, hydrolysis treatment is implemented to outer layer poly (methyl) butyl acrylate so that the outer layer poly (methyl) butyl acrylate has hydrophilicity. Thus, the core-shell type lipophilic-hydrophilic carbon nano tube is obtained. The obtained product has unique amphipathic characteristics in solvent and on the interface of the solvent. The product can be used as nano elements with special functions and a carrier for transferring mass between different systems. Consequently, the product has wide purposes in the aspects of nano science, material science and biomedicine.
Description
Technical field: the preparation method, particularly core-shell type oleophylic-hydrophilic carbon nanotube and preparation method thereof that the present invention relates to a kind of nuclear-shell nanostructure based on carbon nanotube.
Background technology: carbon nanotube (Cabon Nanotube is called for short CNT) is just found a kind of novel carbon structure in 1991, is the body that is rolled into by the Graphene lamella that carbon atom forms.Carbon nanotube be divided into Single Walled Carbon Nanotube (Single-wall Nanotube, SWNT) and multi-walled carbon nano-tubes (Multi-wall Nanotube, MWNT).Its preparation method mainly contains catalyse pyrolysis, arc-over, template and laser evaporation etc.
Because diameter is very little, length-to-diameter ratio is big, carbon nanotube is regarded as quasi-one-dimensional nanometer material.Confirmed now that carbon nanotube has peculiar electric property, superpower mechanical property, good adsorption property, thereby caused very big attention in the material field.The transistor and the indicating meter that have now had carbon nanotube to make come out.
Along with the development of nano science and technology, various carbon nanotubes with specified property cause people's interest gradually.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, various modified carbon nano-tubes and composite structure thereof are produced out.Such as carbon nanotube with solvent solubility, have carbon nano tube device of molecular detection function or the like.
On the other hand, Sawamoto and Matyjaszewski have almost simultaneously found that independently transition metal-catalyzed " activity " controllable free-radical polymerisation of a kind of usefulness is atom transfer radical polymerization (ATRP).This method becomes the research focus of polymer chemistry in the world soon, and is described as " the recent studies on method of 21 century ".This method is to the control of target product with keep and be better than traditional polymerization greatly aspect the lower molecular weight distributing index, also avoided in the traditional method the harsh requirement to the polymerization environment.Simultaneously, because the popularity of initiator, especially, can in product, introduce functional group easily, also can synthesize multiple block polymer with the participation of the initiator of functional group.
Along with science and technology development, have the nanostructure of unique texture and function and the attention that nano-device has obtained people gradually, the annual report that a large amount of this respects are all arranged.Utilize perfect structure of carbon nanotube and excellent performance, exploitation is that the nanostructure and the nano-device of matrix just seems particularly necessary with the carbon nanotube.Utilize the advantage of ATRP method, the combined carbon nanotube just can synthesize various carbon nano tube devices with ad hoc structure, and the application that this can expand above method and material greatly promotes the development of this science and technical field.
Summary of the invention: the objective of the invention is to utilize methods such as atom transfer radical polymerization by molecular designing, preparation core-shell type oleophylic-hydrophilic carbon nanotube satisfies the needs in different application field.
Technical scheme of the present invention is as follows:
By molecular designing, carbon nano tube surface is handled, make it to have the required active group of ATRP polyreaction, thereby can cause the polymerization that contains double bond monomer; At first cause a kind of two monomeric polymerizations of key lipophilicity that contain, form single lipophilicity nucleocapsid structure; Utilize still active initiation center then, cause the monomeric polymerization of the special butyl ester of (methyl) vinylformic acid, it is handled thereupon, hydrophilic radical is exposed, thereby obtain having the core-shell type oleophylic-hydrophilic carbon nanotube of two-layer different sympathy group.
The concrete preparation method of core-shell type oleophylic-hydrophilic carbon nanotube of the present invention is as follows:
Step (a): 1 weight part (quality, exsiccant carbon nanometer tube material and 0.1～100 weight part acid with strong oxidizing property down together), with 0.01～100kHz ultrasonication, 0.1～100hr post-heating to 20～200 ℃, reaction 0.5～100hr, use the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 0～180 ℃ of vacuum-drying 10～30hr;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, behind 0.01～100kHz ultrasonication, 10～1000min, be heated to 20～200 ℃, reaction 0.5～100hr down stirs and refluxes, suction filtration and repetitive scrubbing are removed acylating agent, obtain acylated carbon nano-tube;
Step (c): add step (b) gained acidylate carbon nanotube 1 weight part and polyvalent alcohol or polyamine 1～50 weight part, sealing, take out inflated with nitrogen repeatedly three times, behind 0.01～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has hydroxyl or amido;
Step (d): add carbon nanotube 1 weight part and alpha-halogen carboxylic acid halides 1～50 weight part that step (c) gained surface has hydroxyl or amido, sealing, take out inflated with nitrogen repeatedly three times, behind 0.01～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is after the washing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has initiating group;
Step (e): add 0.01～1 weight part catalyzer, 0.01～5 weight part part, the surface that adds step (d) gained again has carbon nanotube 1 weight part of initiating group, and solvent 0～50 weight part fills Ar or N after the sealing
21～100min, add and contain two key lipophilicity monomer 0.01～80 weight parts, continue inflated with nitrogen or argon gas 1～100min, react 0.01～1000hr down at 0～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in poor solvent, and the gained precipitation heavily is dissolved in good solvent, suction filtration, washing, 0～180 ℃ of vacuum-drying obtains the macromolecular grafted carbon nanotube of single hop lipophilicity;
Step (f): add 0.01～1 weight part catalyzer, 0.01～5 weight part part, add macromolecular grafted carbon nanotube 1 weight part of single hop lipophilicity that step (e) obtains again, solvent 0～50 weight part fills Ar or N after the sealing
21～100min adds the special butyl ester monomer of (methyl) vinylformic acid 0.01～80 weight part, continues inflated with nitrogen or argon gas 1～100min, react 0.01～1000hr down at 0～150 ℃, after viscosity was significantly increased, stopped reaction precipitated in poor solvent, the gained precipitation heavily is dissolved in good solvent, suction filtration, washing, 0～180 ℃ of vacuum-drying, obtaining with the carbon nanotube is nuclear, and bi-block copolymer is the hud typed carbon nanotube structure of shell.
Step (g): add step (f) carbon nanotube that is able to and be nuclear, bi-block copolymer is hud typed carbon nanotube 1 weight part of shell, solvent 0.01～100 weight part, catalyzer 0.01～100 weight part, airtight back is reacted 0.01～1000hr down at 0～100 ℃, solvent and catalyzer are removed, obtained core-shell type oleophylic-hydrophilic carbon nanotube.
Used carbon nanotube is the single wall or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template and the preparation of laser evaporation method in the inventive method step (a).
The used acid with strong oxidizing property of the inventive method step (a) comprises 0.1～70% weight acid concentration nitric acid, 0.1～100% weight acid concentration sulfuric acid, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/10～100/1 mol ratio potassium permanganate and hydrochloric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio H
2O
2With sulfuric acid mixed solution, 1/100～100/1 mol ratio H
2O
2With hydrochloric acid mixed solution, 1/100～100/1 mol ratio H
2O
2With the nitric acid mixing solutions.
Used acylating agent comprises phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide, thionyl bromide in the inventive method step (b).
Polyvalent alcohol or polyamine material used in the inventive method step (c) comprise ethylene glycol, quadrol, glycerol, third triamine, 1, the 2-propylene glycol, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, 1,4-butyleneglycol, 1,4-butanediamine, 1,2-butyleneglycol, 1,2-butanediamine, 1,3 butylene glycol, 1,3-butanediamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol, polyethyene diamine.
Used alpha-halogen carboxylic acid halides comprises alpha-brominated butyryl bromide, alpha-brominated isobutyl acylbromide, alpha-brominated propionyl bromide, alpha-chloro butyryl chloride, alpha-chloro isobutyryl chloride, alpha-chloro propionyl chloride in the inventive method step (d).
Do not use solvent among the inventive method step (c), (d) or with dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine, dimethylamino pyridine are that solvent or the mixed solvent that contains these solvents are reaction medium.
Contain two key lipophilicity monomers in the inventive method step (e) for carrying out the monomer that has non-hydrophilic radical of Raolical polymerizable, comprise methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, the vinylformic acid pentyl ester, Ethyl acrylate, the vinylformic acid heptyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid pentyl ester, N-Hexyl methacrylate, the methacrylic heptyl heptylate, vinylbenzene and derivative thereof (not containing the wetting ability substituting group).
Catalyst system therefor is the metallic compound that contains Cu (I), Fe (II), Mo (V), Re (V), Ru (II), Ni (I), Pb (II) such as cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, ReO in the inventive method step (e), (f)
2I (PPh
3)
2, RuCl
2, Ni (NCN) Br, Pd (OAc)
2Used part is 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine, tri-n-butyl phosphine; Solvent for use is dimethyl sulfoxide (DMSO), N, 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.
Be that solvent or the mixed solvent that contains these solvents are reaction medium with water, methyl alcohol, ethanol, methylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine, dimethylamino pyridine in the inventive method step (g); With hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, trifluoroacetic acid and composition thereof as catalyzer.
Gained core-shell type oleophylic-hydrophilic carbon nanotube prepared in accordance with the present invention is owing to have two-layer different sympathy group, in solvent or the solvent interface show unique amphipathic characteristic, can be used as the nano-device of specific function, construct specific quantum structure; Also can be used as the carrier of material transfer and transfer between different system, realize specific purpose; Thereby have purposes widely at nano science, Materials science and biomedical aspects, great application prospect is arranged.
Description of drawings:
Fig. 1: different samples
1H NMR figure [on: the special butyl ester block polymer of polystyrene and polyacrylic acid grafted carbon nanotube, down: core-shell type oleophylic-hydrophilic carbon nanotube]
Fig. 2: the thermolysis figure of different samples [1, the carbon nanotube of former pipe (crude MWNT) 2, polystyrene graft, 3, the special butyl ester block polymer grafted carbon nanotube (MWNT-PS-b-PtBA) of polystyrene and polyacrylic acid, 4, core-shell type oleophylic-hydrophilic carbon nanotube (MWNT-PS-b-PAA)]
Fig. 3: different samples water (on)-phenomenon in chloroform (descending) system [1, the carbon nanotube (MWNT-PS) of polystyrene graft, 2, the special butyl ester block polymer grafted carbon nanotube (MWNT-PS-b-PtBA) of polystyrene and polyacrylic acid, 3, core-shell type oleophylic-hydrophilic carbon nanotube (MWNT-PS-b-PAA)]
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: the multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is an initial raw material; acidified; after the acidylate; connect ethylene glycol, again with alpha-brominated isobutyryl bromine reaction, with Transfer Radical Polymerization grafting polymethylmethacrylate (PMMA); continue to connect the special butyl ester (PtBA) of polyacrylic acid with Transfer Radical Polymerization again; the special butyl ester hydrolysis treatment of external then strata vinylformic acid makes it possess hydrophilic property, then obtains core-shell type oleophylic-hydrophilic carbon nanotube.
Step (a): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add 2g exsiccant carbon nanometer tube material and 20mL 60% weight ratio concentration concentrated nitric acid, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube behind 80 ℃ of vacuum-drying 24hr with the deionized water repetitive scrubbing;
Step (b): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add step (a) gained acidifying carbon nanotube 1.5g and thionyl chloride 8g, behind 40kHz ultrasonication 30min, be heated to 60 ℃, reaction 24hr down stirs and refluxes, suction filtration and repetitive scrubbing are removed thionyl chloride, obtain acylated carbon nano-tube;
Step (c): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add step (b) gained acidylate carbon nanotube 1.3g and ethylene glycol 25g, seal with the turned welt soft rubber ball, take out inflated with nitrogen repeatedly three times, behind 40kHz ultrasonication 30min, react 24hr down at 100 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, with behind the deionized water wash, 80 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has hydroxyl repeatedly;
Step (d): in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, adding step (c) gained surface has the carbon nanotube 1.1g and the alpha-brominated isobutyl acylbromide 1g of hydroxyl, seal with the turned welt soft rubber ball, take out inflated with nitrogen repeatedly three times, behind 40kHz ultrasonication 30min, at 20 times reaction 1～20hr, suction filtration is removed unreacted reactant and byproduct of reaction, with behind the deionized water wash, 80 ℃ of vacuum-dryings obtain the carbon nanotube that the surface has initiating group repeatedly;
Step (e): in the single neck round-bottomed flask of the 50mL that the magnetic agitation rotor is housed, add 0.6g CuBr, 0.7g part PMDETA (pentamethyl--diethyl triamine), the surface that adds step (d) gained again has the carbon nanotube 1g of initiating group, and solvent DMF 10mL fills N after the sealing
210min adds styrene monomer 10mL, continues to fill N
210min reacts 20hr down at 100 ℃, after viscosity is significantly increased, and stopped reaction, in methyl alcohol, precipitate, the gained precipitation heavily is dissolved in chloroform, suction filtration, washing, remove unreacted monomer and catalyzer etc., 80 ℃ of vacuum-dryings obtain single hop PS grafted carbon nanotube, obtain material 3.2g;
Step (f): in the single neck round-bottomed flask of the 50mL that the magnetic agitation rotor is housed, add 0.4g CuBr, 0.48g part PMDETA, add the PS grafted carbon nanotube 2g that step (e) obtains again, solvent DMF 10mL fills N after the sealing
210min adds the special butyl ester monomer of vinylformic acid 10mL, continues to fill N
210min reacts 10hr down at 50 ℃, after viscosity is significantly increased, and stopped reaction, precipitation in methanol (50/50) heavily is dissolved in DMF with the gained precipitation, suction filtration, washing, remove unreacted monomer and catalyzer etc., 80 ℃ of vacuum-dryings obtain block PS-PtBA grafted carbon nanotube 3.8g;
Step (g): add step (f) carbon nanotube that is able to and be nuclear, bi-block copolymer is the hud typed carbon nanotube 1g of shell, methylene dichloride 10mL, CF
3COOH 0.5g, airtight after stirring reaction 24hr at room temperature, wait the generation post precipitation, solvent and catalyzer are removed, obtain core-shell type oleophylic-hydrophilic carbon nanotube 0.6g.
Fig. 1 provided sample nuclear magnetic spectrogram, clearly shown the feature of two sections polymkeric substance among the figure; A is the characteristic peak of tertiary butyl among the last figure, and after treatment, a disappears, and polyacrylic characteristic peak b (descending) occurred.Fig. 2 has provided the TGA curve of product and intermediate, and as can be seen, different polymer layers have different decomposition temperatures from the figure.Photo among Fig. 3 shows that the carbon nanotube of individual layer lipophilicity PS and undressed two section polymer grafts can only dissolve in chloroform, do not have amphipathic, the finished product core-shell type oleophylic-hydrophilic carbon nanotube then accumulates on the oil-water two-phase interfaces, show amphipathicly, this has proved the performance of product intuitively.
Claims (7)
1. the preparation method of core-shell type oleophylic-hydrophilic carbon nanotube is characterized in that concrete preparation method is as follows:
Step (a): 1 weight part exsiccant carbon nanotube and 0.1～100 weight part acid with strong oxidizing property, with 0.01～100kHz ultrasonication, 0.1～100hr post-heating to 20～200 ℃, reaction 0.5～100hr, use the filter membrane suction filtration, repetitive scrubbing repeatedly to neutral, obtains the acidifying carbon nanotube behind 0～180 ℃ of vacuum-drying 10～30hr; Wherein acid with strong oxidizing property is selected from 0.1～70wt% nitric acid, 0.1～100wt% sulfuric acid, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and hydrochloric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixing solutions, 1/100～100/1 mol ratio hydrogen peroxide and sulfuric acid mixed solution, 1/100～100/1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution or 1/100～100/1 mol ratio hydrogen peroxide and nitric acid mixing solutions;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent 1～100 weight part, behind 0.01～100kHz ultrasonication, 10～1000min, be heated to 20～200 ℃, reaction 0.5～100hr down stirs and refluxes, suction filtration and repetitive scrubbing are removed acylating agent, obtain the acidylate carbon nanotube;
Step (c): add step (b) gained acidylate carbon nanotube 1 weight part and polyvalent alcohol or polyamine 1～50 weight part, sealing, take out inflated with nitrogen repeatedly three times, behind 0.01～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has hydroxyl or amido;
Step (d): add carbon nanotube 1 weight part and alpha-halogen carboxylic acid halides 1～50 weight part that step (c) gained surface has hydroxyl or amido, sealing, take out inflated with nitrogen repeatedly three times, behind 0.01～100kHz ultrasonication, 10～1000min, react 1～20hr down at 20～200 ℃, suction filtration is after the washing, 0～180 ℃ of vacuum-drying obtains the carbon nanotube that the surface has initiating group;
Step (e): add 0.01～1 weight part catalyzer, 0.01～5 weight part part, the surface that adds step (d) gained again has carbon nanotube 1 weight part of initiating group, and solvent 0～50 weight part fills Ar or N after the sealing
21～100min, add and contain two key lipophilicity monomer 0.01～80 weight parts, continue inflated with nitrogen or argon gas 1～100min, react 0.01～1000hr down at 0～150 ℃, after viscosity is significantly increased, stopped reaction precipitates in poor solvent, and the gained precipitation heavily is dissolved in good solvent, suction filtration, washing, 0～180 ℃ of vacuum-drying obtains the macromolecular grafted carbon nanotube of single hop lipophilicity; Wherein catalyzer is selected from cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, iodate oxidation two (triphenyl phosphorus base) rhenium, protochloride nail, bromination nitrogen cyanogen nickel or plumbic acetate; Part is selected from 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine or tri-n-butyl phosphine; Solvent is selected from dimethyl sulfoxide (DMSO), N, 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 its mixed solvent; Contain two key lipophilicity monomers and be selected from methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid heptyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid pentyl ester, N-Hexyl methacrylate, methacrylic heptyl heptylate or vinylbenzene;
Step (f): add 0.01～1 weight part catalyzer, 0.01～5 weight part part, add macromolecular grafted carbon nanotube 1 weight part of single hop lipophilicity that step (e) obtains again, solvent 0～50 weight part fills Ar or N after the sealing
21～100min adds special butyl ester of vinylformic acid or tert-butyl methacrylate monomer 0.01～80 weight part, continues inflated with nitrogen or argon gas 1～100min, react 0.01～1000hr down at 0～150 ℃, after viscosity was significantly increased, stopped reaction precipitated in poor solvent, the gained precipitation heavily is dissolved in good solvent, suction filtration, washing, 0～180 ℃ of vacuum-drying, obtaining with the carbon nanotube is nuclear, and bi-block copolymer is the hud typed carbon nanotube of shell; Wherein catalyzer is selected from cuprous chloride, cuprous bromide, iron protochloride, ferrous bromide, lithium molybdate, iodate oxidation two (triphenyl phosphorus base) rhenium, protochloride ruthenium, bromination nitrogen cyanogen nickel or plumbic acetate; Part is selected from 2-dipyridyl, Tetramethyl Ethylene Diamine, pentamethyl--diethyl triamine, hexamethyl-triethyl tetramine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine or tri-n-butyl phosphine; Solvent is selected from dimethyl sulfoxide (DMSO), N, 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 its mixed solvent;
Step (g): add step (f) carbon nanotube that is able to and be nuclear, bi-block copolymer is hud typed carbon nanotube 1 weight part of shell, solvent 0.01～100 weight part, catalyzer 0.01～100 weight part, airtight back is reacted 0.01～1000hr down at 0～100 ℃, solvent and catalyzer are removed, obtained core-shell type oleophylic-hydrophilic carbon nanotube; Wherein catalyzer is selected from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, trifluoroacetic acid or its mixture; Solvent is selected from water, methyl alcohol, ethanol, methylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine, dimethylamino pyridine or its mixed solvent.
2. the preparation method of core-shell type oleophylic-hydrophilic carbon nanotube according to claim 1 is characterized in that used carbon nanotube is selected from single wall or the multi-walled carbon nano-tubes that catalyse pyrolysis, arc-over, template or laser evaporation method prepare in the step (a).
3. the preparation method of core-shell type oleophylic-hydrophilic carbon nanotube according to claim 1 is characterized in that used acylating agent is selected from phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide in the step (b).
4. the preparation method of core-shell type oleophylic-hydrophilic carbon nanotube according to claim 1 is characterized in that polyvalent alcohol used in the step (c) or polyamine are selected from ethylene glycol, quadrol, glycerol, third triamine, 1,2-propylene glycol, 1,2-propylene diamine, 1, ammediol, 1,3-propylene diamine, 1,4-butyleneglycol, 1,4-butanediamine, 1,2-butyleneglycol, 1,2-butanediamine, 1,3-butyleneglycol, 1,3-butanediamine, trihydroxybutane, fourth triamine, polyoxyethylene glycol or polyethyene diamine.
5. the preparation method of core-shell type oleophylic-hydrophilic carbon nanotube according to claim 1 is characterized in that used alpha-halogen carboxylic acid halides is selected from 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 in the step (d).
6. the preparation method of core-shell type oleophylic-hydrophilic carbon nanotube according to claim 1, it is characterized in that not using among step (c), (d) solvent or with dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, triethylamine, pyridine or dimethylamino pyridine are that solvent or the mixed solvent that contains these solvents are reaction medium.
7. core-shell type oleophylic-hydrophilic carbon nanotube is characterized in that the core-shell type oleophylic-hydrophilic carbon nanotube that adopts each described preparation method of claim 1-6 to obtain.
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| CN100364885C (en) * | 2006-03-09 | 2008-01-30 | 同济大学 | Method for preparing hydrophilic and lipophilic carbon nano tube |
| CN103173041B (en) * | 2013-03-08 | 2014-06-04 | 北京化工大学 | Method for making core-shell polyhedral oligomeric silsesquioxane (POSS) coated multi-walled carbon nanotube (MWNT) |
| CN109179379B (en) * | 2018-11-01 | 2021-11-30 | 中山大学 | Carbon material with nano-network structure and carbon nanotube core @ functional amorphous carbon shell unit, and preparation method and application thereof |
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