CN107445142A - A kind of preparation method of CNT montmorillonite self-assembled nanometer powder - Google Patents

Abstract

The invention discloses a method for preparing carbon nanotube-montmorillonite self-assembled nanopowder. The self-assembled method is as follows: carbon nanotubes are uniformly dispersed in an aprotic organic solvent, and an aminated carbon nanometer is prepared by modifying an organic amine. tube, and modified by protonic acid to prepare carbon nanotube ammonium salt, and set aside; at the same time, montmorillonite is dispersed in water by ultrasonic and stirring, and then the aforementioned carbon nanotube ammonium salt is added, after stirring and washing, spray drying Obtain carbon nanotube-montmorillonite self-assembled nanopowder. The invention self-assembles carbon nanotube ammonium salt and montmorillonite to form a composite of nanoscale one-dimensional/two-dimensional structure, which can realize the insertion of carbon nanotubes between montmorillonite sheets and effectively weaken carbon nanotubes Agglomeration and winding improve its dispersion uniformity in nano-montmorillonite. The carbon nanotube-montmorillonite nanopowder is easy to be industrialized and can be used to design and prepare high-performance polymer composite materials.

Description

A kind of preparation method of carbon nanotube-montmorillonite self-assembled nanopowder

technical field

The invention belongs to the technical field of new materials and their preparation, and in particular relates to a preparation method of carbon nanotube-montmorillonite self-assembled nanopowder.

Background technique

Montmorillonite (MMT) is a layered silicate mineral composed of two layers of silicon-oxygen tetrahedron sandwiched by a layer of aluminum-oxygen octahedron. Thermal stability, ion exchange properties. Blending MMT with polymers can greatly improve the mechanical properties, thermal stability, and barrier properties of composite materials. However, the natural MMT layer spacing is small, and the surface is hydrophilic and oleophobic, which has poor compatibility with polymers and is not conducive to dispersion, which greatly limits the excellent performance of MMT. Usually organic quaternary ammonium salt is used to modify MMT, on the one hand, it can increase the distance between MMT layers, and on the other hand, it can improve its compatibility and dispersion with polymers. However, organic quaternary ammonium salts may decompose at higher processing temperatures, and even promote polymer degradation, which will adversely affect the thermal stability of composite materials. Therefore, it is an urgent problem to find a modifier with high thermal stability to partially or completely replace organic modifiers such as quaternary ammonium salts, and to further increase the interlayer spacing of MMT.

Carbon nanotubes (CNTs) have excellent mechanical, electrical, and thermal properties, and are ideal reinforcement materials for polymer composites. However, due to the high aspect ratio and large specific surface area of CNTs, and the strong van der Waals force between the tubes, it is easy to entangle and agglomerate, and it is difficult to disperse uniformly in the composite material. Some researchers have used the unique lamellar structure of MMT to mix it with CNTs in polymers, thereby weakening the entanglement and agglomeration of CNTs. [Zheng Yuying, Fan Zhimin. A barrier antistatic thermoplastic polyurethane elastomer rubber (TPU) composite film and its preparation method [P].CN 103834051 A.2014] modified by hexadecyltrimethylammonium bromide MMT obtains organic montmorillonite, and then mixes it evenly with amine polycondensate modified CNTs and TPU to obtain a barrier and antistatic film material. In the composite material prepared by the ternary blending method of organic montmorillonite, CNTs and TPU, MMT and CNTs are dispersed in TPU respectively, and the CNTs in it cannot enter the MMT layer, and cannot further promote the interlayer peeling of MMT. In order to further improve the dispersion of CNTs in polymers, CNTs can be intercalated between MMT layers to form a nanoscale one-dimensional/two-dimensional structure composite. Gu Zheng et al [Gu Zheng, Song Guojun, Wang Li, et al. A preparation method of carbon nanotube intercalated montmorillonite reinforced oil-extended emulsion co-coagulation rubber [P].CN104710660 A.2015] Disperse CNTs in water, And mix the same volume of strong acid, add long-chain alkyl ammonium salt or organic quaternary ammonium salt for pretreatment, and then add MMT to stir to obtain CNTs intercalation modified MMT suspension, but the relationship between CNTs and quaternary ammonium salt is mainly through molecular chain entanglement or π- The π-conjugated combination makes the binding force between CNTs and organic montmorillonite weak. In order to improve the binding strength between CNTs and MMT, Manikandan et al [Madaleno L., Pyrz R., Jensen L.R., et al.Synthesis of clay-carbon nanotube hybrids: Growth of carbon nanotubes in different types of iron modifiedmontmorillonite[J].Composites Science and Technology, 2012, 72(3): 377-381] prepared iron-based MMT by cation exchange, and then used chemical vapor deposition to grow CNTs on the surface of iron-based MMT to obtain a composite of MMT and CNTs, although CNTs were growing It is helpful to peel off MMT, but MMT must undergo special treatment such as calcination to make the surface have a catalyst for growing CNTs, and the reaction process requires high temperature, and the treatment process is more complicated. Sedaghat S. et al. [Sedaghat S.Synthesis of clay-CNTs nanocomposite[J].Journal of Nanostructure in Chemistry, 2013, 3(1):1-4] first mixed hexamethylenediamine, hydrochloric acid and MMT to obtain surface with amino groups MMT was dispersed in dimethylformamide organic solvent and carboxylated carbon nanotubes were refluxed at 90°C for 24 hours. The CNTs in the resulting mixture were uniformly dispersed, but the reaction conditions were not mild enough. Therefore, it is of great significance for the industrial application of both to study a preparation method of CNTs intercalation MMT that is easy to control and have mild reaction conditions and make it uniformly dispersed, and it is easy to promote on a large scale.

Contents of the invention

Purpose of the invention: (1) Through the effective intercalation of CNTs to MMT, the interlayer spacing of MMT can be effectively increased, and the problems of easy agglomeration and winding of CNTs and unfavorable dispersion can be solved, so as to prepare carbon nanotubes with excellent characteristics of both MMT and CNTs- Montmorillonite nano-powder; (2) Study a simple and easy-to-control method for preparing carbon nanotube-montmorillonite nano-powder with mild reaction conditions, so as to facilitate industrial and stable production.

Technical solution: In order to achieve the above technical purpose, the present invention proposes a carbon nanotube-montmorillonite self-assembled nanopowder and a preparation method thereof, comprising the following steps:

(1) Aminated carbon nanotubes: Disperse carbon nanotubes in an aprotic organic solvent, add a dehydration condensation agent and an activator, and obtain a carbon nanotube dispersion of 1g/L to 50g/L after stirring and ultrasonication Add the organic amine to the carbon nanotube dispersion to react under stirring, then filter to obtain the aminated carbon nanotube after washing with deionized water and alcohol;

(2) Preparation of carbon nanotube ammonium salt: disperse the aminated carbon nanotubes in step (1) in deionized water to obtain a dispersion of 10g/L～50g/L aminated carbon nanotubes; then use protonic acid to adjust the pH 3.5 to 6.5, stirred, filtered to obtain carbon nanotube ammonium salt, set aside, preferably stirring at a rotating speed of 100r/min to 800r/min for 5h to 48h;

(3) Preparation of carbon nanotube-montmorillonite self-assembled nanopowder: add montmorillonite to deionized water, stir and sonicate, preferably after stirring at 500r/min～1000r/min for 1h～3h, then sonicate for 0.5 h～1h to obtain 10g/L～150g/L montmorillonite suspension; add the carbon nanotube ammonium salt in step (2) to the montmorillonite suspension, and keep stirring, preferably, keep stirring for 1h ~5h; stop stirring, after standing still and settling, wash the precipitate with water for 3-5 times, and finally obtain carbon nanotube-montmorillonite nanopowder by spray drying.

Preferably, the carbon nanotubes in step (1) are single-walled, double-walled or multi-walled carbon nanotubes. More preferably, the surface of the carbon nanotubes has any one or several functional groups among carboxyl groups, acid halides, acid anhydrides and aldehyde groups.

Preferably, in step (1), the organic amine is added to the carbon nanotube dispersion for reaction at room temperature to 50° C. for 5 h to 72 h under stirring at a rotational speed of 100 r/min to 800 r/min.

Preferably, the proton self-transfer reaction of the aprotic organic solvent described in step (1) is extremely weak or does not have self-transfer tendency, and the described aprotic organic solvent is carbon tetrachloride, dichloromethane, dimethyl Any one of sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, acetone, and ether.

Preferably, the dehydration condensation agent described in step (1) is N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide, 1-(3-dimethylamino Propyl)-3-ethylcarbodiimide hydrochloride, benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate, tripyrrolidinylphosphonium bromide hexafluorophosphate, O- (7-Azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, benzotriazole-N,N,N',N'-tetramethylurea Hexafluorophosphate, O-benzotriazole-N,N,N',N'-tetramethyluronium tetrafluoroborate, 6-chlorobenzotriazole-1,1,3,3- Any one of tetramethyluronium hexafluorophosphate O-(1,2-dihydro-2-oxo-pyridyl)-1,1,3,3-tetramethyluronium tetrafluoroborate, dehydrated The condensing agent is 0wt%-5wt% of the carbon nanotube mass. Two kinds of reactions are involved between carbon nanotubes and organic amines in the present invention: 1, the acylation reaction between carboxyl carbon nanotubes and organic amines, this reaction needs dehydration condensation agent, just can accomplish reaction under room temperature, and reaction efficiency High; 2. Carbon nanotubes can be used as dienes or dienophiles to undergo Diels-Alder (Diels-Alder) cycloaddition reaction with organic amines with carbon-carbon double bonds, with mild reaction conditions (generally room temperature to 50°C is enough), no by-products, etc., and no dehydration condensing agent is required to participate in the Diels-Alder reaction.

Preferably, the activator described in step (1) is N-hydroxysuccinimide, N-hydroxyphthalimide, 1-hydroxybenzotriazole, 1-hydroxyl-7-azobenzene Any one in triazole, 4-dimethylaminopyridine, 4-pyrrolidinylpyridine, described activator can activate the carbonyl in carboxyl, suppress the generation of by-product in the reaction system; The consumption of activator is 0wt% to 5wt% of the carbon nanotube mass. Using the dehydrating condensing agent alone is easy to produce by-products, and using the corresponding activator together can inhibit the side reaction and increase the yield, so the combined use of the dehydrating condensing agent and the activator is generally better.

Preferably, the organic amines described in step (1) include but are not limited to ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-diaminopentane, 1,6- Hexamethylenediamine, 1,8-octyldiamine, 1,10-decanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-(3-aminopropyl)-1,4-butyl Diamine, N, N'-bis(3-aminopropyl)-1,4-butanediamine, 2-furylmethylamine, 5-methylfurfurylamine, 2-thiophenemethylamine, thiophene-α-sulfonamide , 5-bromothiophene-2-sulfonamide, 3-aminopropene, acrylamide, 9-octadecylamine, any one or a mixture of several; wherein, the amount of organic amine is 0.5wt% to carbon nanotube mass 10 wt%. The organic amines that can undergo acylation reaction and Diels-Alder cycloaddition reaction with carbon nanotubes are mainly listed here.

Preferably, in step (2), the protonic acid is any one of hydrochloric acid, dilute nitric acid, dilute sulfuric acid, and hydrobromic acid.

Preferably, the cation exchange capacity of the montmorillonite described in step (3) is 60 to 120mmol/100g, and the exchangeable cations in the described montmorillonite are any one or more of sodium, calcium, magnesium and iron. and mixing, the amount of montmorillonite added is 100wt% to 1000wt% of the mass of carbon nanotubes.

Preferably, in step (3), the ammonium salt of carbon nanotubes in step (2) is added to the montmorillonite suspension at a speed of 0.05g/min～2g/min, at a speed of 200r/min～600r/min Continue to stir for 1h to 5h.

Basic principle of the present invention: In the present invention, carbon nanotubes and organic amines are first prepared by acylation reaction or Diels-Alder reaction to prepare carbon nanotubes containing amino segments, and then react with protonic acid to form carbon nanotubes Ammonium salt, and finally, the ammonium salt of carbon nanotubes is exchanged with montmorillonite through cation exchange, so that carbon nanotubes are intercalated into the montmorillonite sheet, and finally a carbon nanotube-montmorillonite self-assembly with a one-dimensional/two-dimensional structure is formed Nano powder. The nanopowder has both the excellent properties of montmorillonite and carbon nanotubes. On the one hand, intercalation of carbon nanotubes can increase the layer spacing of montmorillonite, and can replace the traditional long-chain alkyl quaternary ammonium salt with low thermal stability; on the other hand, , the sheet structure of montmorillonite can block and weaken the entanglement of carbon nanotubes, thereby improving the dispersion of carbon nanotubes. Moreover, organic amines are combined with carbon nanotubes through covalent bonds to enhance the interfacial interaction between carbon nanotubes and montmorillonite.

Beneficial effects: compared with the prior art, the present invention has the following technical effects:

(1) The carbon nanotube-montmorillonite nanopowder of the present invention utilizes the barrier property of lamellar montmorillonite to effectively improve the dispersion of carbon nanotubes, reduce or avoid the phenomenon that carbon nanotubes are easy to entangle and agglomerate;

(2) The carbon nanotube-montmorillonite nanopowder of the present invention improves the interlayer distance of montmorillonite through carbon nanotube intercalation, so that its excellent performance can be brought into play, and can partially or completely replace the traditional long chain with low thermal stability. Alkyl modifier;

(3) The interfacial bonding between the carbon nanotube and montmorillonite is strong, good in stability, mild in reaction conditions, high in raw material utilization, environmentally friendly, and capable of large-scale production.

(4) The carbon nanotube-montmorillonite nanopowder of the present invention has both excellent properties, and can be used as a new type of composite reinforcement to improve the performance of polymer composite materials, with broad application prospects.

Description of drawings

Fig. 1 is the infrared spectrum (FT-IR) figure before and after organic amine modification carbon nanotube;

Fig. 2 is the microscopic topography figure (SEM) and elemental analysis (EDS) before and after carbon nanotube intercalation montmorillonite in embodiment 1;

Fig. 3 is the X-ray diffraction (XRD) figure of carbon nanotube intercalation montmorillonite nanopowder;

Fig. 4 is the SEM figure of carbon nanotube intercalation montmorillonite nanopowder in embodiment 2 example;

Fig. 5 is the SEM figure of carbon nanotube intercalation montmorillonite nanopowder in embodiment 3 examples;

Fig. 6 is the SEM figure of carbon nanotube intercalation montmorillonite nanopowder in embodiment 4 examples;

Fig. 7 is the SEM figure of carbon nanotube intercalation montmorillonite nanopowder in embodiment 5 examples;

FIG. 8 is an SEM image of carbon nanotube intercalated montmorillonite nanopowder in Example 6. FIG.

detailed description

The above content of the present invention will be further described in detail below through specific examples. However, it should not be construed that the content of the present invention is limited to the following examples.

Example 1

A preparation method of carbon nanotube-montmorillonite self-assembled nanopowder, the specific steps are as follows:

(1) Aminated carbon nanotubes: Weigh 0.2g of carboxyl carbon nanotubes and add them to 0.02L of N,N'-dimethylformamide solvent, then add 0.005g of N,N'-diisopropyl carbon Diimine and 1-hydroxybenzotriazole were stirred for 5 minutes and ultrasonicated for 30 minutes to obtain a 10 g/L carbon nanotube dispersion liquid, which was magnetically stirred at a speed of 200 r/min; weighed 0.01 g of diethylenetriamine Add it to the carbon nanotube dispersion, react at room temperature for 24 hours, wash with deionized water and alcohol twice, and then filter to obtain diethylenetriamine-modified carbon nanotubes;

(2) Preparation of carbon nanotube ammonium salt: the carbon nanotube modified by diethylenetriamine in step (1) was stirred in 0.02L deionized water for 5min, ultrasonically for 30min to obtain 10g/L aminocarbon nanotube dispersion, Use hydrochloric acid (protonic acid) to adjust the pH to about 4.5, and stir at a rotating speed of 300r/min for 24h to obtain the carbon nanotube ammonium salt, which is set aside;

(3) Carbon nanotube intercalated montmorillonite: Dissolve 1g of montmorillonite (cation exchange capacity 90mmol/100g) in 50ml of deionized water, stir for 1.5h, and sonicate for 0.5h to obtain 20g/L montmorillonite suspension Add the ammonium salt of carbon nanotubes in step (2) at a speed of 0.05g/min, and stir magnetically for 3h at a speed of 400r/min: after standing for settling, washing and filtering with deionized water for 3 to 5 times, and finally spray drying The carbon nanotube intercalation montmorillonite nanopowder is obtained.

Figure 1 is the FT-IR images before and after organic amine modification of carbon nanotubes. It can be seen from Figure 1 that, compared with carboxyl carbon nanotubes, the nanopowder of this example presents two double peaks at 3447cm- ¹ and 3417cm ^-1 , presumably the overlapping stretching vibration peaks of _-NH2 or -NH-, and 1633cm ^- 1 ¹ is the in-plane bending vibration peak of -NH-, and 785cm ^-1 is the out-of-plane bending vibration peak of -NH-; 1717cm ^-1 and 1159cm ^-1 are the stretching vibration peaks of -C=O and -CN- respectively; double The peaks at 2934cm ^-1 and 2860cm ^-1 correspond to the stretching vibration peaks of -CH ₂ -. It can be seen that carboxyl multi-walled carbon nanotubes and diethylenetriamine are mainly combined through amide bonds. Fig. 2 is the SEM microscopic morphology and EDS elemental analysis before and after carbon nanotube intercalation with montmorillonite in this embodiment. It can be seen from Figure 2(c) that carbon nanotubes are uniformly dispersed on the surface of montmorillonite; from the comparison of atomic percentages in Figure 2(b) and (d), it can be seen that after carbon nanotubes are combined with montmorillonite, N elements appear on the surface, and The total atomic percentage of elements Mg and Ca decreased, which indicated that the cation exchange between carbon nanotube ammonium salt and montmorillonite was successful. Fig. 3 is an XRD pattern of carbon nanotube intercalated montmorillonite nanopowder. It can be seen from Figure 3 that the 2θ angle of curve (b) is reduced from 7.08° to 5.66°. It can be seen from the calculation of the Bragg equation (2dsinθ=nλ) that the interlayer spacing of montmorillonite increases after intercalation of carbon nanotubes, which shows that the intercalation of ammonium salts of carbon nanotubes into montmorillonite is successful.

Example 2

A preparation method of carbon nanotube-montmorillonite self-assembled nanopowder, which is different from Example 1 in that the carboxyl carbon nanotubes described in step (1) become 0.5g, and the N, N' -Diisopropylcarbodiimide and 1-hydroxybenzotriazole become 0.01g respectively, and the organic amine becomes 0.1g triethylenetetramine; pH value is adjusted to 4 with hydrochloric acid in step (2) ; The carbon nanotube ammonium salt described in the step (3) in the montmorillonite suspension has a stirring speed of 600r/min. It can be seen from Figure 1 that the carboxyl multi-walled carbon nanotubes and triethylenetetramine are combined through amide bonds. It can be seen from Fig. 3 that the 2θ angle of the nanopowder in this example is reduced from 7.08° to 5.57°, it can be seen that the interlayer distance of montmorillonite increases after intercalation of carbon nanotubes, and the intercalation of carbon nanotubes into montmorillonite is successful. Fig. 4 is an SEM image of the carbon nanotube intercalated montmorillonite nanopowder prepared in this example, wherein Fig. 4(b) is a partial enlarged view of Fig. 4(a). It can be seen from Figure 4 that carbon nanotubes are uniformly dispersed on the surface of montmorillonite.

Example 3

A carbon nanotube-montmorillonite self-assembled nanopowder and preparation method thereof, its difference from Example 1 is that the carboxyl carbon nanotubes described in step (1) become 1g, and the aprotic organic Solvent becomes carbon tetrachloride, and described dehydration condensation agent becomes 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxyl succinimide ( NHS), described organic amine becomes 0.05g tetraethylenepentamine; Protonic acid described in step (2) becomes dilute nitric acid, adjusts pH to be 3.5, and described rotating speed is transferred to 600r/min; Step (3) The quality of the montmorillonite described in becomes 5g, the cation exchange capacity of the montmorillonite becomes 100mmol/100g, and the stirring speed of the carbon nanotube ammonium salt in the montmorillonite suspension is 600r/min. It can be seen from Figure 1 that the carboxyl multi-walled carbon nanotubes and tetraethylenepentamine are combined through amide bonds. It can be seen from Fig. 3 that the 2θ angle of the nanopowder in this example is reduced from 7.08° to 5.58°, it can be seen that the interlayer spacing of montmorillonite increases after intercalation of carbon nanotubes, and the intercalation of carbon nanotubes into montmorillonite is successful. FIG. 5 is an SEM image of the carbon nanotube intercalated montmorillonite nanopowder prepared in this example. It can be seen from Figure 5 that carbon nanotubes are uniformly dispersed on the surface of montmorillonite.

Example 4

A carbon nanotube-montmorillonite self-assembled nanopowder and a preparation method thereof, which differ from Example 1 in that the aprotic organic solvent described in step (1) becomes an acetone solvent, and the organic amine Substance becomes 0.02g of 1,8-octanediamine, and the dehydration condensation agent becomes 0.01g hexafluorophosphate benzotriazol-1-yl-oxyl tripyrrolidinylphosphine (PyBOP); step ( 2) the protonic acid described in becomes hydrobromic acid; The montmorillonite described in step (3) becomes 4g montmorillonite, and the cation exchange capacity of montmorillonite becomes 70mmol/100g, and described carbon nanometer The stirring speed of tube ammonium salt in montmorillonite suspension is 600r/min. It can be seen from Figure 1 that the carboxyl multi-walled carbon nanotubes and 1,8-octanediamine are combined through amide bonds. It can be seen from Fig. 3 that the angle of 20 of the nanopowder in this example is reduced from 7.08° to 5.58°. It can be seen that the interlayer spacing of montmorillonite increases after intercalation of carbon nanotubes, and the intercalation of carbon nanotubes into montmorillonite is successful. FIG. 6 is an SEM image of the carbon nanotube intercalated montmorillonite nanopowder prepared in this example. It can be seen from Figure 6 that carbon nanotubes are uniformly dispersed on the surface of montmorillonite.

Example 5

A carbon nanotube-montmorillonite self-assembled nanopowder and a preparation method thereof, which differ from Example 1 in that the surface of the carbon nanotube described in step (1) has no active functional groups, and the quality of the carbon nanotube becomes 0.5 The aprotic organic solvent described in g becomes dimethyl sulfoxide solvent, the described dehydration condensation agent becomes 0 g, and the described organic amines become 0.02 g of 2-furylamine, and react at 50° C. 48h; the pH value described in the step (2) is adjusted to 5.5; The carbon nanotube ammonium salt described in the step (3) turns the stirring speed into 300r/min in the montmorillonite suspension, and the stirring time becomes 8h . It can be seen from Figure 1 that the nanopowder of this example still has two double peaks at 3447cm ^-1 and 3417cm ^-1 after being washed with a large amount of water, which is speculated to be the -NH stretching vibration peak, and ^{1633cm -1} _is the plane of -NH- Inner bending vibration peak, and 785cm ^-1 is the out-of-plane bending vibration peak of -NH-; 1159cm ^-1 is the stretching vibration peak of -CN-; double peaks 2934cm ^-1 and 2860cm ^-1 correspond to the stretching vibration peak of -CH ₂ - . It can be seen that the Diels-Alder cycloaddition reaction between multi-walled carbon nanotubes and 2-furylamine has been successful. It can be seen from Fig. 3 that the 2θ angle of the nanopowder in this example is reduced from 7.08° to 5.68°, it can be seen that the interlayer spacing of montmorillonite increases after intercalation of carbon nanotubes, and the intercalation of carbon nanotubes into montmorillonite is successful. FIG. 7 is an SEM image of the carbon nanotube intercalated montmorillonite nanopowder prepared in this example. It can be seen from Figure 7 that carbon nanotubes are uniformly dispersed on the surface of montmorillonite.

Example 6

A carbon nanotube-montmorillonite self-assembled nanopowder and preparation method thereof, which differ from Example 1 in that the surface of the carbon nanotube described in step (1) has no active functional groups, and the quality of the carbon nanotube becomes 1g , the aprotic organic solvent becomes hexamethylphosphoric triamide, the dehydration condensation agent becomes 0g, the organic amines become 0.04g of 3-aminopropene, react at 50°C 36h; the protonic acid described in step (2) becomes dilute sulfuric acid, and the pH value is adjusted to 5; the carbon nanotube ammonium salt described in step (3) becomes 200r/m in the montmorillonite suspension The min stirring time was changed to 6h. It can be seen from Figure 1 that the nanopowder of this example still has two double peaks at 3447cm ^-1 and 3417cm ^-1 after being washed with a large amount of water, which is speculated to be the -NH stretching vibration peak, and ^{1633cm -1} _is the plane of -NH- Inner bending vibration peak, and 785cm ^-1 is the out-of-plane bending vibration peak of -NH-; 1159cm ^-1 is the stretching vibration peak of -CN-; double peaks 2934cm ^-1 and 2860cm ^-1 correspond to the stretching vibration peak of -CH ₂ - . It can be seen that the Diels-Alder reaction between multi-walled carbon nanotubes and 2-furylamine has been successful. It can be seen from Fig. 3 that the 2θ angle of the nanopowder in this example is reduced from 7.08° to 5.59°, it can be seen that the interlayer spacing of montmorillonite increases after intercalation of carbon nanotubes, and the intercalation of carbon nanotubes into montmorillonite is successful. FIG. 8 is an SEM image of the carbon nanotube intercalated montmorillonite nanopowder prepared in this example. It can be seen from Figure 8 that carbon nanotubes are uniformly dispersed on the surface of montmorillonite.

Claims (10)

1. a preparation method of carbon nanotube-montmorillonite self-assembled nanopowder, is characterized in that, comprises the steps: (1) Aminated carbon nanotubes: Disperse carbon nanotubes in an aprotic organic solvent, add a dehydration condensation agent and an activator, and obtain a carbon nanotube dispersion of 1g/L to 50g/L after stirring and ultrasonication ; keep stirring and add the organic amine to the carbon nanotube dispersion to react, then wash with deionized water, wash with alcohol, and then filter to obtain the aminated carbon nanotube; (2) Preparation of carbon nanotube ammonium salt: disperse the aminated carbon nanotubes in step (1) in deionized water to obtain a dispersion of 10g/L～50g/L aminated carbon nanotubes; then use protonic acid to adjust the pH 3.5 to 6.5, stirred, filtered to obtain carbon nanotube ammonium salt, set aside; (3) Preparation of carbon nanotube-montmorillonite self-assembled nanopowder: add montmorillonite to deionized water, stir and sonicate to obtain montmorillonite suspension of 10g/L～150g/L; The carbon nanotube ammonium salt in 2) is added to the montmorillonite suspension, and the stirring is continued; the stirring is stopped, and after standing and settling, the precipitate is washed with water, and finally the carbon nanotube-montmorillonite nanopowder is obtained by spray drying. 2. the preparation method of carbon nanotube-montmorillonite nanopowder according to claim 1, is characterized in that, the carbon nanotube described in step (1) is the carbon nanotube of single wall, double wall or multiwall . 3. the preparation method of carbon nanotube-montmorillonite nanopowder according to claim 1 is characterized in that, in step (1), under the stirring of rotating speed 100r/min～800r/min, organic amine is added carbon nanometer React in the tube dispersion solution, and react at room temperature to 50°C for 5h to 72h. 4. the preparation method of carbon nanotube-montmorillonite self-assembly nanopowder according to claim 1, is characterized in that, the proton self-delivery reaction of the aprotic organic solvent described in step (1) is extremely weak or does not have Self-transfer tendency, described aprotic organic solvent is carbon tetrachloride, methylene dichloride, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, acetone, Any of the ethers. 5. the preparation method of carbon nanotube-montmorillonite self-assembly nanopowder according to claim 1, is characterized in that, the dehydration condensation agent described in step (1) is N, N '-dicyclohexyl carbon di Imine, N,N'-diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, benzotriazole-1 hexafluorophosphate -yl-oxytripyrrolidinylphosphine, tripyrrolidinylphosphonium bromide hexafluorophosphate, O-(7-azobenzotriazole)-N,N,N',N'-tetramethylurea Hexafluorophosphate, benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate, O-benzotriazole-N,N,N',N'-tetramethyl Urea tetrafluoroborate, 6-chlorobenzotriazole-1,1,3,3-tetramethyluronium hexafluorophosphate O-(1,2-dihydro-2-oxo-pyridyl) Any one of 1,1,3,3-tetramethylurea tetrafluoroborate, the dehydration condensation agent is 0wt%-5wt% of the carbon nanotube mass. 6. the preparation method of carbon nanotube-montmorillonite self-assembly nanopowder according to claim 1, is characterized in that, the activator described in step (1) is N-hydroxyl succinimide, N-hydroxyl Any one of phthalimide, 1-hydroxybenzotriazole, 1-hydroxy-7-azobenzotriazole, 4-dimethylaminopyridine, 4-pyrrolidinylpyridine, activated The dosage of the agent is 0wt%-5wt% of the carbon nanotube mass. 7. the preparation method of carbon nanotube-montmorillonite self-assembly nanopowder according to claim 1, is characterized in that, the organic amine described in step (1) is ethylenediamine, 1,3-propylenediamine , 1,4-butanediamine, 1,5-diaminopentane, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, diethylenetriamine, triethylenetetra Amine, tetraethylenepentamine, N-(3-aminopropyl)-1,4-butanediamine, N,N'-bis(3-aminopropyl)-1,4-butanediamine, 2-furan Any of methylamine, 5-methylfurfurylamine, 2-thienylmethylamine, thiophene-α-sulfonamide, 5-bromothiophene-2-sulfonamide, 3-aminopropene, acrylamide, and 9-octadecenylamine One or more mixtures; wherein, the amount of organic amine is 0.5wt%-10wt% of the mass of carbon nanotubes. 8. the preparation method of carbon nanotube-montmorillonite self-assembly nanopowder according to claim 1, is characterized in that, in step (2), described protonic acid is hydrochloric acid, dilute nitric acid, dilute sulfuric acid, hydrogen bromide any acid. 9. the preparation method of carbon nanotube-montmorillonite self-assembly nanopowder according to claim 1, is characterized in that, the cation exchange capacity of the montmorillonite described in step (3) is 60～120mmol/100g, The exchangeable cation in the montmorillonite is any one or a combination of several of sodium, calcium, magnesium and iron, and the amount of the montmorillonite added is 100wt%-1000wt% of the carbon nanotube mass. 10. the preparation method of carbon nanotube-montmorillonite self-assembly nanopowder according to claim 1, is characterized in that, in step (3), the carbon nanotube ammonium salt in step (2) is with 0.05g/ Add it into the montmorillonite suspension at a speed of 200r/min~600r/min, and keep stirring for 1h~5h at a speed of 200r/min~600r/min.