CN1286717C - Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method - Google Patents
Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method Download PDFInfo
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- CN1286717C CN1286717C CN 200410017699 CN200410017699A CN1286717C CN 1286717 C CN1286717 C CN 1286717C CN 200410017699 CN200410017699 CN 200410017699 CN 200410017699 A CN200410017699 A CN 200410017699A CN 1286717 C CN1286717 C CN 1286717C
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Abstract
The present invention provides a functional carbon nanometer tube with isocyanate radicals on the surface and a preparation method thereof. After a carbon nanometer tube is treated by strong oxidative acid, the carbon nanometer tube reacts with thionyl chloride so as to obtain a product which reacts with binary ammonia or dibasic alcohol to obtain a modification carbon nanometer tube with amino groups or hydroxy groups on the surface. The modification carbon nanometer tube with amino groups or hydroxy groups on the surface reacts with binary isocyanate or multiple isocyanate so as to the functional carbon nanometer tube with isocyanate radials on the surface. The functional carbon nanometer tube with isocyanate radials on the surface has favorable reaction reactivity, and can further react with substances containing amino groups and hydroxy groups, and thereby, the functional carbon nanometer tube with isocyanate radials on the surface can be used as an important intermediate body. Other substances (such as polyureas, polyurethane, etc.) are connected to the outer surface of the carbon nanometer tube through the chemical reaction so as to design, prepare and use new nanometer materials.
Description
Technical field: the present invention relates to a kind of preparation method of functionalized carbon nano-tube, particularly the surface has functionalized carbon nano-tube of isocyanate groups and preparation method thereof.
Background technology: carbon nanotube (Carbon 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 graphite flake layer that carbon atom forms.Quantity according to its graphite flake layer, carbon nanotube is divided into Single Walled Carbon Nanotube (Single-walled Carbon Nanotube, SWNT), double-walled carbon nano-tube (Double-walled Carbon Nanotube, DWNT), and multi-walled carbon nano-tubes (Multi-walledCarbon Nanotube, MWNT).
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.
On the other hand, because carbon nanotube does not dissolve, make its processing difficulties in organic solvent and water, this has limited its application in a lot of fields greatly, also makes troubles for deeply understanding carbon nanotube chemical.For this reason, arise at the historic moment (Science, 1998,280 (22): 1253-1255) of the organic functional of carbon nanotube research.
At present, with synthetic polymer, biomacromolecule and contain the organic molecule or the metal complex of functional group, the method that connects by physical adsorption or covalency has been carried out modification or functionalization work to the pipe end of carbon nanotube outside surface or single-wall carbon tube.But also there is not the surface to contain the report of the functionalized carbon nano-tube of isocyanate groups at present.Because isocyanate groups has very high reactive behavior, if can allow the surface of carbon nanotube connect this group, then as intermediate, can prepare many new function carbon nano tube materials.
Summary of the invention: the objective of the invention is to pass through chemical reaction, make the organic compound that has isocyanate groups be connected to carbon nano tube surface, the preparation surface has the functionalized carbon nano-tube of isocyanate groups, thereby can be used as a kind of important intermediate nano material, satisfy the needs of different research work and Application Areas.
Technical scheme of the present invention is as follows:
By molecular designing, the surface is had the modified carbon nano-tube of amino or hydroxyl and excessive binary or multicomponent isocyanate reaction, obtain the functionalized carbon nano-tube that the surface has isocyanate groups.
The concrete preparation method of the functionalized carbon nano-tube of the present invention surface isocyanate groups is as follows:
Step (a): carbon nanotube is mixed with acid with strong oxidizing property with 0.1～100 weight ratio, with the 40-100kHz ultrasonication after 2 minutes to 2 hours, 20～200 ℃ are stirred down, reacted 0.5～100 hour, suction filtration, the water repetitive scrubbing repeatedly is neutral to filtrate, obtains the acidifying carbon nanotube after the vacuum-drying;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent thionyl chloride 1～100 weight part, with the 40-100kHz ultrasonication after 3～60 minutes, be heated to 20～160 ℃, stir reaction down 5～100 hours, suction filtration and repetitive scrubbing are removed acylating agent, obtain acylated carbon nano-tube; Gained acidylate carbon nanotube 1 weight part is mixed with polyvalent alcohol or polyamine 1～50 weight part, after 3～100 minutes, reacted 1～50 hour down at 0～200 ℃ with the 40-100kHz ultrasonication, suction filtration, behind the repetitive scrubbing, vacuum-drying obtains the surface and has hydroxyl or amino carbon nanotube;
Step (c): it is 20/1～1/100 reinforced with weight ratio that above gained surface is had the modified carbon nano-tube of amino or hydroxyl and multicomponent isocyanate, add organic solvent again, reacted 2～120 hours down in-30～100 ℃, after filtration, washing, vacuum-drying obtains the functionalized carbon nano-tube that the surface has isocyanate groups; Wherein multicomponent isocyanate is selected from isophorone diisocyanate, tolylene diisocyanate, 4,4 '-ditan-vulcabond, hexamethylene diisocyanate, fourth vulcabond, hot vulcabond, the last of the ten Heavenly stems vulcabond, naphthalene diisocyanate or three (to isocyanate phenyl) methane.
The used carbon nanotube of the present invention is selected from single wall, double-walled or multi-walled carbon nano-tubes.
The used organic solvent of reaction is selected from dimethyl sulfoxide (DMSO), N in the step of the present invention (c), dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, dioxy hexanaphthene, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, benzene, toluene, oil of mirbane, chlorinated benzene or its mixture.
Surface provided by the invention has the functionalized carbon nano-tube of isocyanate groups in polar organic solvent such as dimethyl sulfoxide (DMSO), N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, has good dispersiveness in the N-N-methyl-2-2-pyrrolidone N-etc., its surperficial isocyanate groups has reactive behavior, can be further and amino, hydroxyls etc. react, also can react with excessive diamines or glycol, surperficial isocyanate groups is converted into amino or hydroxyl, thereby can realize material and molecular designing in carbon nano tube surface easily, thereby obtain various functionalized carbon nano-tube and relevant nano-devices with special construction and performance, can also be used as linking agent, for the preparation high performance material provides a kind of reactive behavior high intermediate, have a wide range of applications.
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, 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 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;
In the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add above 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;
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 quadrol 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 1.1g that the surface has amido repeatedly;
In the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add 5g 4,4 '-ditan-vulcabond (MDI) and 50mL N, the N-N,N-DIMETHYLACETAMIDE, after treating the solid dissolving, flask is placed ice/water-bath, and the surface that adding 0.3g prepares in advance has amino modified carbon nano-tube.Stirring reaction 2h under ice/water-bath, ultrasonic 5 minutes, heat to 40 ℃, continue reaction 24h.Decompress filter is used 200mLN, and N-N,N-DIMETHYLACETAMIDE washing leaching cake 4 times is used tetrahydrofuran (THF) 200mL washing leaching cake 4 times again, obtains target product behind 40 ℃ of vacuum-drying 5h.
Embodiment 2: in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add 5g hexamethylene diisocyanate (HDI) and 50mLN, the N-N,N-DIMETHYLACETAMIDE is after the dissolving, flask is placed ice/water-bath, and the surface that adding 0.3g prepares in advance has amino modified carbon nano-tube.Stirring reaction two 2h under ice/water-bath, ultrasonic 5 minutes, heat to 40 ℃, continue reaction 48h.Decompress filter is used 200mL N,N-dimethylacetamide washing leaching cake 4 times, uses tetrahydrofuran (THF) 200mL washing leaching cake 4 times again, obtains target product behind 40 ℃ of vacuum-drying 5h.
Embodiment 3: in the single neck round-bottomed flask of the 100mL that the magnetic agitation rotor is housed, add 2g hexanediamine and 20mLN, the N-N,N-DIMETHYLACETAMIDE is after the dissolving, flask is placed ice/water-bath, add the functionalized carbon nano-tube that 0.1g embodiment 1 prepared surface has isocyanate groups.Stirring reaction is two 10 minutes under ice/water-bath, and ultrasonic 5 minutes, heat to 50 ℃, continue reaction 48h.Decompress filter is used 200mLN, and N-N,N-DIMETHYLACETAMIDE washing leaching cake 4 times is used tetrahydrofuran (THF) 200mL washing leaching cake 4 times again, obtains the surface behind 40 ℃ of vacuum-drying 5h and has amino functionalized carbon nano-tube.This embodiment illustrates that the isocyanate groups that the prepared surface of the present invention has on the functionalized carbon nano-tube of isocyanate groups still has chemically reactive, can continue to take place chemical reaction.
Claims (4)
1. the surface has the preparation method of the functionalized carbon nano-tube of isocyanate groups, it is characterized in that its concrete preparation method is as follows:
Step (a): carbon nanotube is mixed with acid with strong oxidizing property with 0.1～100 weight ratio, with the 40-100kHz ultrasonication after 2 minutes to 2 hours, 20～200 ℃ are stirred down, reacted 0.5～100 hour, suction filtration, the water repetitive scrubbing repeatedly is neutral to filtrate, obtains the acidifying carbon nanotube after the vacuum-drying;
Step (b): add step (a) gained acidifying carbon nanotube 1 weight part and acylating agent thionyl chloride 1～100 weight part, with the 40-100kHz ultrasonication after 3～60 minutes, be heated to 20～160 ℃, stir reaction down 5～100 hours, suction filtration and repetitive scrubbing are removed acylating agent, obtain acylated carbon nano-tube; Gained acidylate carbon nanotube 1 weight part is mixed with polyvalent alcohol or polyamine 1～50 weight part, after 3～100 minutes, reacted 1～50 hour down at 0～200 ℃ with the 40-100kHz ultrasonication, suction filtration, behind the repetitive scrubbing, vacuum-drying obtains the surface and has hydroxyl or amino carbon nanotube;
Step (c): it is 20/1～1/100 reinforced with weight ratio that above gained surface is had the modified carbon nano-tube of amino or hydroxyl and multicomponent isocyanate, add organic solvent again, reacted 2～120 hours down in-30～100 ℃, after filtration, washing, vacuum-drying obtains the functionalized carbon nano-tube that the surface has isocyanate groups; Wherein multicomponent isocyanate is selected from isophorone diisocyanate, tolylene diisocyanate, 4,4 '-ditan-vulcabond, hexamethylene diisocyanate, fourth vulcabond, hot vulcabond, the last of the ten Heavenly stems vulcabond, naphthalene diisocyanate or three (to isocyanate phenyl) methane.
2. surface according to claim 1 has the preparation method of the functionalized carbon nano-tube of isocyanate groups, it is characterized in that used carbon nanotube is selected from single wall, double-walled or multi-walled carbon nano-tubes.
3. surface according to claim 1 has the preparation method of the functionalized carbon nano-tube of isocyanate groups, it is characterized in that used organic solvent is selected from dimethyl sulfoxide (DMSO), N in the step (c), dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, dioxy hexanaphthene, chloroform, tetrahydrofuran (THF), ethyl acetate, acetone, acetonitrile, butanone, benzene, toluene, oil of mirbane, chlorinated benzene or its mixture.
4. the surface has the functionalized carbon nano-tube of isocyanate groups, it is characterized in that the surface of adopting each described preparation method of claim 1-3 to obtain has the functionalized carbon nano-tube of isocyanate groups, is used as nanometer linking agent and nano material intermediate.
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