CN1844176A - Process for in-situ synthesis of amphiphilic polymer modified carbon nanotube - Google Patents
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Abstract
This invention belongs to material technology. Exactly speaking, it's the preparation of amphipathy-polymer modified carbon nanometer tube with original position systhesis. Supersonic assistance purifies the carbon nanometer tube raw material in acid conditions. At certain temperature, N-Vinyl-2-Pyrrolidone occur polyreaction in original positon and graft to the surface of carbon nanometer tube in the presence of initiator. After that, the grafted carbon nanometer tube with hydrophobic groups and hydrophilic groups on its surface is obtained. Such carbon nanometer tube has good dispersity in water, organic solvent and polymer base. This invention is advantageous in simplified-manipulation, controllability, quantification. Our product could be used in composite material, hydrogen gas storage, electronic device, sensors and biological materials and so on.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of preparation method of in-situ synthesis of amphiphilic polymer modified carbon nanotube.
Technical background
Carbon nanotube (CNTs) since being found by Japanese scholar Iijima in 1991, with its distinctive mechanics, electricity and chemical property and unique accurate one dimension tracheary element structure and the many potential using value that in following high-tech area, is had, become the research focus of chemistry, physics and material science rapidly.
CNTs has very big length-to-diameter ratio, generally greater than 1000.The Young's modulus of CNTs is identical with diamond, and theoretical strength can reach 1.0TPa, is 100 times of steel; The calculated value of carbon nanotube tensile strength is up to 177GPa, far above carbon fiber (2GPa～5GPa), whisker (20GPa) and high-strength steel (1GPa～2GPa).The axial Young's modulus experimental value of multi-walled carbon nano-tubes is 200GPa～4000GPa, and axial bending intensity is 14GPa, and axial compression strength is 100GPa, and has the toughness (theoretical maximum unit elongation can reach 20%) of superelevation, and density only is 1/7 of steel.Carbon nanotube has broad prospects in the application in matrix material, hydrogen storage, electron device, battery, ultracapacitor, Field Emission Display, quantum lead template, electron beam gun and fields such as transmitter and microscope probe.Although carbon nanotube has been obtained significant progress in the applied research of every field, these use desirable in to realize existing very big difficulty.Because the CNTs surface energy is high, between the tube and tube greatly the Van der Waals force effect make it assemble bunchy easily, and be dissolved in any solvent hardly, therefore be difficult to be distributed in matrices of composite material or the various application system, this is the bottleneck that the restriction carbon nanotube is used.And the key of opening this bottleneck is modified carbon nano tube surface exactly, makes its surface-functionalized, groupization, reduces surface energy, increases surfactivity.Polyvinylpyrolidone (PVP) (PVP) is a kind of superpolymer with special construction, the methylene radical of pyrrolidone ring is a non-polar group, has lipophilicity, lactan in the molecule is strong polar group, has hydrophilic interaction, so the water-soluble and many organic solvents of its energy, as alkane, alcohol, carboxylic acid, amine, chlorinated hydrocarbon etc.If PVP can be incorporated into carbon nano tube surface, its good solubility can obviously be improved the dispersing property of carbon nanotube in water, organic solvent and polymeric matrix.Therefore study a kind of quantitatively the introducing in carbon nano tube surface and have hydrophilic and polymkeric substance lipophilic group, the method for utilizing this structure to improve the dispersiveness of carbon nanotube in water, organic solvent and polymeric matrix is those skilled in the art's a goal in research.
Summary of the invention
The object of the present invention is to provide the preparation method of simple, the easy to operate in-situ synthesis of amphiphilic polymer modified carbon nanotube of a kind of technology.
The preparation method of the in-situ synthesis of amphiphilic polymer modified carbon nanotube that the present invention proposes, method by in-situ polymerization, make the carbon nano tube surface behind the purifying carry out graft reaction, under action of evocating, carbon nano tube surface is introduced to be had hydrophilic and polymkeric substance lipophilic group, obtains the surface and has have better dispersed carbon nano tube in water and organic solvent; Its concrete steps are as follows:
(1) carbon nanotube 1 weight part and organic acid 10～150 weight parts are mixed, under 0～100kHz ultrasonic wave, reacted 0.1～100 hour, be heated to 20～100 ℃ then, reacted 0.1～100 hour, with the microfiltration membrane suction filtration, repeatedly to neutral, vacuum-drying is 5～48 hours under 20～200 ℃ of temperature, obtains the carbon nanotube of purifying for repetitive scrubbing;
(2) purifying carbon nano-tube 1 weight part that step (1) is obtained, reactive monomer vinyl pyrrolidone (NVP) 1～100g, organic solvent 10～250ml, account for the initiator of monomer vinyl pyrrolidone weight 0.2%～2.0%, place the single port flask respectively, mix and stir, under 0～100kHz ultrasonic wave, vibrated 0.1～100 hour, then under 50～150 ℃, back flow reaction 2～100 hours; Solution for vacuum suction filtration to after the polymerization obtains powder, with the washing of gained powder, suction filtration, until monomer, polymers grafted is not removed fully, vacuum-drying, be 2～20 hours time of drying, temperature is 20～180 ℃, and vacuum tightness is 0.1～1kPa, promptly gets desired product.
Among the present invention, the carbon nanotube described in the step (1) is the single wall or the multi-walled carbon nano-tubes of arc discharge method, chemical Vapor deposition process and the preparation of laser evaporation method.
Among the present invention, organic acid described in the step (1) comprises in hydrochloric acid of 1～30% weight acid concentration nitric acid, 1～50% weight acid concentration sulfuric acid, 0.1～40% weight acid concentration etc. any.
Among the present invention, organic solvent described in the step (2) be in water, ethanol, acetone, chloroform, tetrahydrofuran (THF) or the dimethyl formamide etc. any.
Among the present invention, initiator described in the step (2) be in dibenzoyl peroxide (BPO), the own ester of peroxy dicarbonate dihexyl (EHP), Diisopropyl azodicarboxylate (AIBN) or the 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) etc. any.
Utilize the application of modified carbon nano-tube that the inventive method makes in fields such as matrix material, hydrogen storage, electron device, transmitter, biomaterials.
The product that utilizes the inventive method to make, the polymer content on its carbon nanotube can adopt certain detection means to detect, but as can TGA, XPS nuclear magnetic resonance method etc.
Preparation method provided by the invention is simple, has the characteristics of controllability and quantification; The surface of gained has the carbon nanotube of quantitative amphiphilic polymkeric substance, in water, organic solvent and polymeric matrix, show good 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
Fig. 1 is a kind of in-situ synthesis of amphiphilic polymer modified carbon nanotube infrared tube spectrogram.Wherein, (a) be purifying carbon nano-tube; (b) carbon nanometer-tube decorated with amphipathic nature polyalcohol that utilizes the inventive method to obtain.
Fig. 2 is a kind of in-situ synthesis of amphiphilic polymer modified carbon nanotube thermogravimetric analysis curve.Wherein, (a) be purifying carbon nano-tube; (b) carbon nanometer-tube decorated with amphipathic nature polyalcohol that utilizes the inventive method to obtain.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: with the multi-walled carbon nano-tubes of chemical Vapor deposition process preparation (OD＜8nm) be an initial raw material, pass through purifying after, under action of evocating, then obtain the graft type multi-walled carbon nano-tubes that Polyvinylpyrolidone (PVP) (PVP) is contained on the surface.
Step (1): in the single neck round-bottomed flask of churned mechanically 250ml is housed, add 2g multi-walled carbon nano-tubes raw material and 100mL, 20% weight concentration salpeter solution, under the 40kHz ultrasonic wave, handled 24 hours, be heated to 50 ℃ then, reacted 30 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.45 μ m, extremely neutral with the deionized water repetitive scrubbing, 80 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 24 hours;
Step (2): in churned mechanically 250ml three neck round-bottomed flasks are housed, the purifying carbon nano-tube 0.5g, 150ml acetone, 20gNVP, the 1.0gBPO that add step (1) gained, after 60 minutes, be heated to 80 ℃ with the 40Hz ultrasonication, back flow reaction is 24 hours under stirring, suction filtration and repetitive scrubbing, remove unreacted monomer and graftomer not, the vacuum-drying time is 16 hours, and temperature is 100 ℃, vacuum tightness is 0.8kPa, obtains amphiphilic polymer modified carbon nanotube;
Fig. 1 has provided in-situ synthesis of amphiphilic polymer modified carbon nanotube infrared tube spectrogram, as can be seen from the figure in the carbon nanotube grafting amphipathic nature polyalcohol.
Fig. 2 is an in-situ synthesis of amphiphilic polymer modified carbon nanotube thermogravimetric analysis curve, and the amount that can draw carbon nano tube surface introducing amphipathic nature polyalcohol from thermogravimetric curve is 12.2%.
Embodiment 2: with the Single Walled Carbon Nanotube of arc discharge method preparation (OD＜8nm) be an initial raw material, pass through purifying after, under action of evocating, then obtain the graft type Single Walled Carbon Nanotube that Polyvinylpyrolidone (PVP) (PVP) is contained on the surface.
Step (1): in the single neck round-bottomed flask of churned mechanically 250ml is housed, add 1g Single Walled Carbon Nanotube raw material and 200mL, the sulfuric acid of 30% weight concentration, with 80kHz ultrasonication 12 hours, be heated to 80 ℃ then, reacted 10 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.45 μ m, to neutral, 100 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 18 hours with the deionized water repetitive scrubbing;
Step (2): in churned mechanically 250ml three neck round-bottomed flasks are housed, the purifying carbon nano-tube 0.5g, 100ml dehydrated alcohol, 10gNVP, the 0.5g AIBN that add step (1) gained, with the 80Hz ultrasonication after 30 minutes, be heated to 100 ℃, stirred down back flow reaction 12 hours, suction filtration and repetitive scrubbing are removed unreacted monomer and graftomer not, the vacuum-drying time is 8 hours, temperature is 170 ℃, and vacuum tightness is 0.3KPa, obtains amphiphilic polymer modified carbon nanotube;
Its thermogravimetric result shows that Single Walled Carbon Nanotube Facially amphilic polymers introducing amount is 10.3%;
Embodiment 3: with the multi-walled carbon nano-tubes of arc discharge method preparation (OD＜8nm) be an initial raw material, pass through purifying after, under action of evocating, then obtain the graft type multi-walled carbon nano-tubes that Polyvinylpyrolidone (PVP) (PVP) is contained on the surface.
Step (1): in the single neck round-bottomed flask of churned mechanically 500ml is housed, add 2g multi-walled carbon nano-tubes raw material and 250mL, 30% weight concentration hydrochloric acid, with 100kHz ultrasonication 10 hours, be heated to 30 ℃ then, reacted 80 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.45 μ m, to neutral, 50 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 48 hours with the deionized water repetitive scrubbing;
Step (2): in churned mechanically 250ml three neck round-bottomed flasks are housed, the purifying carbon nano-tube 0.5g, 150ml chloroform, 40gNVP, the 2.0gEHP that add step (1) gained, behind 100Hz ultrasonication 20min, be heated to 120 ℃, stirred down back flow reaction 8 hours, suction filtration and repetitive scrubbing are removed unreacted monomer and graftomer not, the vacuum-drying time is 4 hours, temperature is 180 ℃, and vacuum tightness is 0.1KPa, obtains amphiphilic polymer modified carbon nanotube;
The amount that can draw carbon nano tube surface introducing amphipathic nature polyalcohol from thermogravimetric curve is 11.7%.
Embodiment 4: with the multi-walled carbon nano-tubes of laser evaporation method preparation (OD＜8nm) be an initial raw material, pass through purifying after, under action of evocating, then obtain the graft type multi-walled carbon nano-tubes that Polyvinylpyrolidone (PVP) (PVP) is contained on the surface.
Step (1): in the single neck round-bottomed flask of churned mechanically 250ml is housed, add 2.5g multi-walled carbon nano-tubes raw material and 200mL, 20% weight concentration salpeter solution, with 30kHz ultrasonication 24 hours, be heated to 100 ℃ then, reacted 0.5 hour, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.45 μ m, to neutral, 90 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 24 hours with the deionized water repetitive scrubbing;
Step (2): in churned mechanically 250ml three neck round-bottomed flasks are housed, the purifying carbon nano-tube 0.5g, 150ml dimethyl formamide, 30gNVP, the 1.5gBPO that add step (1) gained, behind 30Hz ultrasonication 80min, be heated to 120 ℃, stirred down back flow reaction 15 hours, suction filtration and repetitive scrubbing are removed unreacted monomer and graftomer not, the vacuum-drying time is 12 hours, temperature is 150 ℃, and vacuum tightness is 0.6KPa, obtains amphiphilic polymer modified carbon nanotube;
The amount that can draw carbon nano tube surface introducing amphipathic nature polyalcohol from thermogravimetric curve is 14.7%.
Claims (6)
1, a kind of preparation method of in-situ synthesis of amphiphilic polymer modified carbon nanotube, it is characterized in that passing through in-situ polymerization, make the carbon nano tube surface behind the purifying carry out graft reaction, under action of evocating, carbon nano tube surface is introduced to be had hydrophilic and polymkeric substance lipophilic group, and its concrete steps are as follows:
(1) carbon nanotube 1 weight part and organic acid 10～150 weight parts are mixed, under 0～100kHz ultrasonic wave, reacted 0.1～100 hour, be heated to 20～100 ℃ then, reacted 0.1～100 hour, with the microfiltration membrane suction filtration, washing is to neutral, and vacuum-drying is 5～48 hours under 20～200 ℃ of temperature, obtains the carbon nanotube of purifying;
(2) purifying carbon nano-tube 1 weight part that step (1) is obtained, reactive monomer vinyl pyrrolidone 1～100g, organic solvent 10～250ml, account for the initiator of monomer vinyl pyrrolidone weight 0.2%～2.0%, place the single port flask respectively, mix and stir, under 0～100kHz ultrasonic wave, vibrated 0.1～100 hour, then under 50～150 ℃, back flow reaction 2～100 hours; Solution for vacuum suction filtration to after the polymerization obtains powder, with the washing of gained powder, suction filtration, until monomer, polymers grafted is not removed fully, vacuum-drying, be 2～20 hours time of drying, temperature is 20～180 ℃, and vacuum tightness is 0.1～1kPa, promptly gets desired product.
2, the preparation method of in-situ synthesis of amphiphilic polymer modified carbon nanotube according to claim 1 is characterized in that described carbon nanotube is single wall or multi-walled carbon nano-tubes.
3, the preparation method of in-situ synthesis of amphiphilic polymer modified carbon nanotube according to claim 1, it is characterized in that described organic acid be in the hydrochloric acid of 1～30% weight acid concentration nitric acid, 1～50% weight acid concentration sulfuric acid or 0.1～40% weight acid concentration any.
4, the preparation method of in-situ synthesis of amphiphilic polymer modified carbon nanotube according to claim 1, it is characterized in that described organic solvent be in water, ethanol, acetone, chloroform, tetrahydrofuran (THF) or the dimethyl formamide any.
5, the preparation method of in-situ synthesis of amphiphilic polymer modified carbon nanotube according to claim 1, it is characterized in that described initiator be in dibenzoyl peroxide, the own ester of peroxy dicarbonate dihexyl, Diisopropyl azodicarboxylate or the 2,2'-Azobis(2,4-dimethylvaleronitrile) any.
6, the modified carbon nano-tube that obtains of a kind of preparation method as claimed in claim 1 is in the application of matrix material, hydrogen storage, electron device, transmitter, technical field of biological material.
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