CN109279595B - Preparation method of aliphatic amine modified carbon nano tube - Google Patents
Preparation method of aliphatic amine modified carbon nano tube Download PDFInfo
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- -1 aliphatic amine modified carbon nano tube Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 claims description 18
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000002310 reflectometry Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 229960001124 trientine Drugs 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 238000002715 modification method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of fatty amine modified carbon nano-tubes, which comprises the following steps: respectively dissolving aliphatic amine and nitrite in a solvent to obtain two solutions, and precooling the two solutions for later use; adding a carbon nano tube into a solvent, adding a small amount of acid, and controlling the temperature to be-80-20 ℃; and (3) dripping the pre-cooled aliphatic amine solution and nitrite solution into a mixture of the carbon nano tube, a small amount of acid and a solvent for reaction, recovering the solvent after the reaction is finished, and filtering and washing to obtain the aliphatic amine modified carbon nano tube. The method has the advantages of simple process operation and high product yield, improves the wave absorption of the product, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of manufacturing of modified carbon nanotubes, in particular to a preparation method of an aliphatic amine modified carbon nanotube.
Background
Carbon nanotubes have unique structure, mechanical and electrical properties, and are widely applied in the fields of light, electricity, magnetism, biology and the like. However, the production application is limited by the defect that the carbon nanotubes are easy to aggregate in a solution during the using and modifying processes. In recent years, much research has been devoted to the development of novel adsorbents. Some groups are attached to the carbon nanotubes for improved adsorption and recovery. Carboxyl, amino, sulfonic group and other groups are introduced on the carbon nano tube, so that the dispersibility of the carbon nano tube in the solution can be improved, and the research for improving the adsorbability and selectivity of the carbon nano tube becomes a new hotspot.
In addition, the carbon nano tube shows certain wave-absorbing performance, the science and technology of China are continuously developed, the wave-absorbing requirement is continuously improved, and the improvement of the wave-absorbing performance of the carbon nano tube material becomes one of hot spots. The modified carbon nano tube is dispersed and compounded to form, so that the wave absorption performance of the modified carbon nano tube can be improved, and the performance of the modified carbon nano tube for absorbing micromolecular pollutants is enhanced. Common modification methods include a doping modification method and a chemical reaction modification method, and because the hydrophilicity of the carbon nanotube is not high and the modification method is not mature enough, the modification method for safely connecting the amine group to the carbon nanotube is a difficult problem in current research.
Therefore, in combination with the above problems, it is an urgent need to provide a method for preparing an aliphatic amine modified carbon nanotube having high wave-absorbing property and good adsorption property by stably linking an amine group to a carbon nanotube.
Disclosure of Invention
In view of the above, the invention provides a preparation method of an aliphatic amine modified carbon nanotube, which has the advantages of simple process operation, high product yield, improved wave absorption of the product, and suitability for large-scale industrial production.
The invention forms stable chemical bond by the reaction of carbocation ions and carbon nano tubes, and connects amidocyanogen with the carbon nano tubes to obtain the amine modified carbon nano tubes, wherein the reaction equation is as follows:
R’ONO+RCH2NH2→RCH2N2 ++R’OH
RCH2N2 +→RCH2 ++N2
RCH2 ++R”C＝CR”→R”C-C(R”)CH2R
in order to achieve the purpose, the technical scheme adopted by the invention is as follows:
s1, dissolving the fatty amine in the solvent, and precooling the obtained solution for later use;
s2, dissolving nitrite in a solvent, and precooling the obtained solution for later use;
s3, adding the carbon nano tube into a solvent, adding a small amount of acid, and controlling the temperature to be-80-20 ℃;
s4, adjusting the volumes of S1 and S2 by using a solvent to ensure that the volumes of the S1 and the S2 are equal, simultaneously and quickly dripping the two mixed solutions obtained in the steps S1 and S2 into the mixture of the carbon nano tube, the acid and the solvent obtained in the step S3, stirring, controlling the temperature to react after finishing dripping, naturally returning to the room temperature after the reaction is finished, recovering the solvent, and filtering and washing to obtain the aliphatic amine modified carbon nano tube;
wherein the solvent is one or a mixture of two or more of acetonitrile, tetrahydrofuran and diethyl ether;
the reaction is carried out under the protection of inert gas.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
according to the technical scheme, the aliphatic amine reacts with the carbon nano tube to form a stable chemical bond, and the amine group is connected to the carbon nano tube, so that the dispersibility of the carbon nano tube is improved, the carbon nano tube is prevented from being unevenly distributed during copolymerization, and the yield of a product is improved; slowly dropwise adding, so that the reaction is carried out at low temperature and low concentration, and the accumulation of unstable intermediates is avoided; fully stirring to ensure that the unstable intermediate is quickly diffused and reacted; the technical scheme of the invention avoids explosion, ensures that the reaction can be smoothly and safely carried out, the product yield reaches over 80 percent, and the final product and the raw materials are easy to separate. The method can prepare a large amount of amino modified carbon nano tubes at normal temperature, and is suitable for large-scale industrial production.
Preferably, the aliphatic amine in step S1 includes, but is not limited to, 1, 4-cyclohexanediamine, diethylenetriamine, triethylenetetramine.
Preferably, the nitrite in step S2 is isopropyl nitrite or methyl nitrite.
Preferably, the acid in step S3 includes, but is not limited to, malonic acid, benzoic acid.
Preferably, the pre-cooling treatment in the steps S1 and S2 is carried out, and the temperature is controlled to be-80-20 ℃.
Preferably, the reaction temperature in the step S4 is controlled to be-80-20 ℃.
Preferably, the dropping time in the step S4 is 0.1-4 h.
Preferably, the reaction time in the step S4 is 5-24 h.
Preferably, the ratio of the amount of carbon to the amount of the aliphatic amine in the carbon nanotubes is 1:0.01 to 100.
Preferably, the amount of the aliphatic amine and the nitrite are equal.
In conclusion, the technical scheme disclosed by the invention enhances the dispersibility of the carbon nano tube, ensures that the carbon nano tube is not easy to gather into bundles in the solution, connects the aliphatic amine to the carbon nano tube, increases the fat solubility of the aliphatic chain, enhances the water solubility and the modifiability of the amino group, overcomes the problem that the amino group and the carbon nano tube cannot be stably connected, is favorable for the development and the application of low-concentration metal ion enrichment, and provides a candidate material for developing a wave-absorbing material.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment 1 of the invention discloses a preparation method of an aliphatic amine modified carbon nano tube, which adopts the following technical scheme:
s1, dissolving 0.33moL (37.7g) of 1, 4-cyclohexanediamine in acetonitrile serving as a solvent, wherein the volume ratio of the 1, 4-cyclohexanediamine to the acetonitrile is 1:8 to obtain a 1, 4-cyclohexanediamine solution, controlling the temperature to be-80 ℃, and pre-cooling for later use;
s2, dissolving 0.33moL (31.0g) of isopropyl nitrite in acetonitrile serving as a solvent, wherein the volume ratio of the isopropyl nitrite to the acetonitrile is 1:8, obtaining an isopropyl nitrite solution, controlling the temperature to be 80 ℃ below zero, pre-cooling for later use, adding a small amount of acetonitrile serving as the solvent, and adjusting the volumes of the 1, 4-cyclohexanediamine solution and the isopropyl nitrite solution to be equal;
s3, under the protection of nitrogen, selecting a 500mL round-bottom bottle, placing 4g of carbon nano tube, 50mL of acetonitrile and 0.033moL (3.4g) of malonic acid, and controlling the temperature to be-50 ℃;
and S4, simultaneously, dripping the solution obtained in the step S1 and the solution obtained in the step S2 into the mixture of the carbon nano tube, the acid and the solvent obtained in the step S3 at the same speed, stirring, controlling the temperature to be 50 ℃ below zero, dripping for about 0.5h, reacting for 12h after dripping is finished, naturally returning to the room temperature after the reaction is finished, recovering the solvent, filtering and washing to obtain the amino modified carbon nano tube.
The yield of the amino modified carbon nanotube prepared in this example is 80%, a sample is subjected to a performance test, and the results of the adsorption performance and the wave absorbing performance test are shown in tables 1 and 2.
Example 2:
the embodiment 2 of the invention discloses a preparation method of an aliphatic amine modified carbon nano tube, which adopts the following technical scheme:
s1, dissolving 0.6moL (61.8g) of diethylenetriamine in a solvent tetrahydrofuran, wherein the volume ratio of the diethylenetriamine to the tetrahydrofuran is 1:10, obtaining a diethylenetriamine solution, controlling the temperature to be-75 ℃, and pre-cooling for later use;
s2, dissolving 0.6moL (36.6g) of methyl nitrite in a solvent tetrahydrofuran, wherein the volume ratio of the methyl nitrite to the tetrahydrofuran is 1:10, obtaining a methyl nitrite solution, controlling the temperature to be-75 ℃, pre-cooling for standby, supplementing a small amount of solvent tetrahydrofuran, and adjusting the volume of a diethylenetriamine solution and the volume of the methyl nitrite solution to be equal;
s3, under the protection of nitrogen, selecting a 500mL round-bottom bottle, putting 2g of carbon nano tube, 20mL of tetrahydrofuran and 0.06moL (7.3g) of benzoic acid, and controlling the temperature to be-55 ℃;
and S4, simultaneously, dripping the solution obtained in the step S1 and the solution obtained in the step S2 into the mixture of the carbon nano tube, the acid and the solvent obtained in the step S3 at the same speed, stirring, controlling the temperature to be 55 ℃ below zero, dripping for about 2.5 hours, reacting for 16 hours after dripping is finished, naturally returning to the room temperature after the reaction is finished, recovering the solvent, and filtering and washing to obtain the diethylenetriaminopropyl carbon nano tube.
The yield of the diethylenetriamine-based carbon nanotube prepared in this example is 84%, a sample is subjected to a performance test, and the results of the adsorption performance and the wave-absorbing performance test are shown in tables 1 and 2.
Example 3:
the embodiment 3 of the invention discloses a preparation method of an aliphatic amine modified carbon nano tube, which adopts the following technical scheme:
s1, dissolving 1.25moL (182g) of triethylene tetramine in a solvent of diethyl ether, wherein the volume ratio of the triethylene tetramine to the diethyl ether is 1:15, obtaining a triethylene tetramine solution, controlling the temperature to be-70 ℃, and pre-cooling for later use;
s2, dissolving 1.25moL (117.1g) of isopropyl nitrite in a solvent of ethyl ether, wherein the volume ratio of the isopropyl nitrite to the ethyl ether is 1:15, obtaining an isopropyl nitrite solution, controlling the temperature to be-70 ℃, pre-cooling for later use, adding a small amount of solvent of ethyl ether, and adjusting the volumes of a triethylene tetramine solution and an isopropyl nitrite solution to be equal;
s3, under the protection of nitrogen, selecting a 500mL round-bottom bottle, placing 3g of carbon nano tube, 30mL of ether and 0.1moL (16.6g) of phthalic acid, and controlling the temperature to react at-40 ℃;
and S4, simultaneously, dripping the solution obtained in the step S1 and the solution obtained in the step S2 into the mixture of the carbon nano tube, the acid and the solvent obtained in the step S3 at the same speed, stirring, controlling the temperature to be minus 40 ℃, dripping for about 4 hours, reacting for 24 hours after dripping is finished, naturally returning to the room temperature after the reaction is finished, recovering the solvent, and filtering and washing to obtain the triethylene tetramine based carbon nano tube.
The yield of the triethylene tetraamine-based carbon nanotube prepared in the embodiment is 86%, a sample is subjected to a performance test, and the results of the adsorption performance and the wave absorbing performance test are shown in tables 1 and 2.
Example 4:
the embodiment 4 of the invention discloses a preparation method of an aliphatic amine modified carbon nano tube, which adopts the following technical scheme:
s1, dissolving 1.0moL (114g) of 1, 4-cyclohexanediamine in tetrahydrofuran serving as a solvent, wherein the volume ratio of the 1, 4-cyclohexanediamine to the tetrahydrofuran is 1:10 to obtain a 1, 4-cyclohexanediamine solution, controlling the temperature to be-10 ℃, and pre-cooling for later use;
s2, dissolving 1.0moL (93.7g) of isopropyl nitrite in tetrahydrofuran solvent, wherein the volume ratio of the isopropyl nitrite to the tetrahydrofuran is 1:10, obtaining isopropyl nitrite solution, controlling the temperature to be 10 ℃ below zero, pre-cooling for later use, adding a small amount of tetrahydrofuran solvent, and adjusting the volume of the 1, 4-cyclohexanediamine solution and the volume of the isopropyl nitrite solution to be equal;
s3, under the protection of nitrogen, selecting a 500mL round-bottom bottle, placing 0.12g of carbon nano tube, 20mL of tetrahydrofuran and 0.1moL (16.6g) of terephthalic acid, and reacting at-80 ℃ under the controlled temperature;
and S4, simultaneously dripping the solutions obtained in the steps S1 and S2 into the mixture of the carbon nano tube, the acid and the solvent obtained in the step S3 at the same speed, stirring, controlling the temperature to be 80 ℃ below zero, dripping for about 4 hours, reacting for 24 hours after dripping is finished, naturally returning to the room temperature after the reaction is finished, recovering the solvent, and filtering and washing to obtain the amino modified carbon nano tube.
The yield of the amino modified carbon nanotube prepared in this example is 92%, a sample is subjected to a performance test, and the results of the adsorption performance and the wave absorbing performance test are shown in tables 1 and 2.
Example 5:
the embodiment 5 of the invention discloses a preparation method of an aliphatic amine modified carbon nano tube, which adopts the following technical scheme:
s1, dissolving 0.01moL (1.14g) of 1, 4-cyclohexanediamine in a solvent of diethyl ether, wherein the volume ratio of the 1, 4-cyclohexanediamine to the diethyl ether is 1:5 to obtain a 1, 4-cyclohexanediamine solution, controlling the temperature to be 20 ℃, and pre-cooling for later use;
s2, dissolving 0.01moL (0.937g) of isopropyl nitrite in a solvent ether, wherein the volume ratio of the isopropyl nitrite to the ether is 1:5, obtaining an isopropyl nitrite solution, controlling the temperature to be 20 ℃, pre-cooling for later use, adding a small amount of solvent ether, and adjusting the volumes of the 1, 4-cyclohexanediamine solution and the isopropyl nitrite solution to be equal;
s3, under the protection of nitrogen, selecting a 500mL round-bottom bottle, placing 12g of carbon nano tube, 10mL of diethyl ether and 0.001moL (0.166g) of isophthalic acid, and controlling the temperature to react for 20 ℃;
and S4, simultaneously, dripping the solution obtained in the step S1 and the solution obtained in the step S2 into the mixture of the carbon nano tube, the acid and the solvent obtained in the step S3 at the same speed, stirring, controlling the temperature to be 20 ℃, dripping for about 0.1 hour, reacting for 5 hours after dripping is finished, naturally returning to the room temperature after the reaction is finished, recovering the solvent, and filtering and washing to obtain the amino modified carbon nano tube.
The yield of the amino modified carbon nanotube prepared in this example is 87%, a sample is subjected to a performance test, and the results of the adsorption performance and the wave absorbing performance test are shown in tables 1 and 2.
Example 6:
the aliphatic amine modified carbon nanotubes prepared in examples 1 to 5 were subjected to performance testing, and the data of the testing results are shown in tables 1 to 2:
TABLE 1 recovery of methylene blue by adsorption for sample stability testing
| Sample (I) | Number of uses 3 | Number of uses 5 | Number of uses 7 | Number of uses 9 |
| Example 1 | 96％ | 94％ | 92％ | 89％ |
| Example 2 | 96％ | 95％ | 93％ | 91％ |
| Example 3 | 97％ | 94％ | 93％ | 88％ |
| Example 4 | 98％ | 97％ | 95％ | 94％ |
| Example 5 | 81％ | 79％ | 74％ | 72％ |
The percentages are based on the first adsorption capacity.
Although the adsorption capacity of the samples was slightly decreased as the number of cycles was increased, the samples of examples 1 to 5 exhibited good adsorption performance as a whole. The sample of example 5 has a significant decrease in adsorption capacity with increasing cycle number, and the sample of example 3 has the best adsorption capacity.
The samples of examples 1 to 5 were prepared as coaxial test samples with paraffin wax in a ratio of 1:2, respectively, and then tested at a frequency range of 1 to 18GHz using a vector network analyzer, and the test results at a sample thickness of 2.8mm are shown in Table 2.
TABLE 2 wave-absorbing Properties
| Sample (I) | Minimum value of reflectivity | Bandwidth with reflectivity less than-10 dB |
| Example 1 | -53dB | 7.2GHz |
| Example 2 | -50dB | 6.9GHz |
| Example 3 | -52dB | 7.0GHz |
| Example 4 | -46dB | 6.4GHz |
| Example 5 | -45dB | 6.2GHz |
When the thickness of a sample is 2.8mm, the minimum value of the reflectivity of the sample in the embodiment 1 reaches-53 dB, the bandwidth with the reflectivity less than-10 dB reaches 7.2GHz, and the sample has better wave-absorbing performance; in the embodiment 2, the minimum value of the reflectivity of the sample reaches-50 dB, the bandwidth with the reflectivity less than-10 dB reaches 6.9GHz, and the sample has good wave-absorbing performance; in the embodiment 3, the minimum value of the reflectivity of the sample reaches-52 dB, the bandwidth with the reflectivity less than-10 dB reaches 7.0GHz, and the sample has better wave-absorbing performance; in the embodiment 4, the minimum value of the reflectivity of the sample reaches-46 dB, the bandwidth with the reflectivity less than-10 dB reaches 6.9GHz, and the sample has good wave-absorbing performance; in the embodiment 5, the minimum value of the reflectivity of the sample reaches-45 dB, the bandwidth with the reflectivity less than-10 dB reaches 6.2GHz, and the sample has better wave-absorbing performance; the samples of the embodiments 1-5 of the invention basically meet the requirements of the wave-absorbing material of being thin, light, wide and strong.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of an aliphatic amine modified carbon nanotube is characterized by comprising the following specific steps:
s1, dissolving the fatty amine in the solvent, and precooling the obtained solution for later use;
s2, dissolving nitrite in a solvent, and precooling the obtained solution for later use;
s3, adding the carbon nano tube into a solvent, adding a small amount of acid, and controlling the temperature to be-80-20 ℃;
s4, adjusting the volumes of S1 and S2 by using a solvent to ensure that the volumes of the S1 and the S2 are equal, simultaneously and quickly dripping the two mixed solutions obtained in the steps S1 and S2 into the mixture of the carbon nano tube, the acid and the solvent obtained in the step S3, stirring, controlling the temperature to react after finishing dripping, naturally returning to the room temperature after the reaction is finished, recovering the solvent, and filtering and washing to obtain the aliphatic amine modified carbon nano tube;
wherein the solvent is one or a mixture of more than two of acetonitrile, tetrahydrofuran and diethyl ether;
the reaction is carried out under the protection of inert gas.
2. The method of claim 1, wherein the aliphatic amine in step S1 is 1, 4-cyclohexanediamine, diethylenetriamine, or triethylenetetramine.
3. The method as claimed in claim 1, wherein the nitrite in step S2 is isopropyl nitrite or methyl nitrite.
4. The method as claimed in claim 1, wherein the acid in step S3 is malonic acid or benzoic acid.
5. The method for preparing aliphatic amine modified carbon nanotubes as claimed in claim 1, wherein the pre-cooling treatment in steps S1 and S2 is performed at a temperature of-80 to 20 ℃; in the step S4, the reaction temperature is controlled to be-80-20 ℃.
6. The method for preparing aliphatic amine modified carbon nanotubes as claimed in claim 1, wherein the dropping time in step S4 is 0.1-4 h.
7. The method for preparing aliphatic amine modified carbon nanotubes as claimed in claim 1, wherein the reaction time in step S4 is 5-24 h.
8. The method of claim 1, wherein the ratio of the amount of the carbon to the amount of the aliphatic amine in the carbon nanotube is 1:0.01 to 100, and the amount of the aliphatic amine is equal to the amount of the nitrite.
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| CN1775839A (en) * | 2005-12-15 | 2006-05-24 | 上海交通大学 | Method for preparing carbon nano tube/rubber nano composite matcrial by non-acidation treatment |
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