CN101264881B - A kind of cyclodextrin-carbon nanotube derivative and its preparation method - Google Patents

Abstract

The invention discloses a cyclodextrin-carbon nanotube derivative, which is characterized in that the rude carbon nanotube is processed with milling, purification and acidification, then the carbon nanotube is reacted with a halogenation reagent; the carboxylic acid radical at the surface of carbon nanotube is transformed to acyl halide radical which has strong reactivity; then the carbon nanotube is reacted with a binary functional group organic compound; the active functional group is extended out of the surface of carbon nanotube and reacted with trichloro-triazine; the carbon nanotube containing the active chlorine triazine ring is obtained, and the active chlorine triazine ring is positioned on the surface of the carbon nanotube and can be reacted with hydroxyl; finally, the invention is prepared by the nucleophilic substitution reaction between the carbon nanotube and the cyclodextrin. In the invention, the mass ratio of cyclodextrin and carbon nanotube is about 0.1-0.8:1. The invention also discloses the preparation method of the cyclodextrin-carbon nanotube derivative. The cyclodextrin-carbon nanotube derivative has the advantages of friendly environment, good solubility in dimethyl sulfoxide, N-methylpyrrolidone, N,N'-dimethylformamide and N,N'-dimethylacetamide, easily satisfied preparation condition, abundant material source and low cost.

Description

A kind of cyclodextrin-carbon nanotube derivative and its preparation method

technical field

The invention relates to a derivative, in particular to a cyclodextrin-carbon nanotube derivative and a preparation method of the derivative, which belongs to the field of natural polymers and also belongs to the field of nanometer materials.

Background technique

In 1991, Japanese scientist Iijima S. discovered carbon nanotubes (Iijma S. Discovery of carbon nano-tubes. Kagaku to Kogyo, 1993, 67(12): 500-506). After more than ten years of development, carbon nanotubes have become an important research frontier of nanotechnology, and its major research results have emerged one after another, occupying a pivotal position in the development of science and technology in the 21st century. The peculiar quasi-one-dimensional hollow tube structure of carbon nanotubes makes it have excellent performance in many aspects such as adsorption, electricity, magnetism, field emission, mechanics, and electrochemistry. However, the extremely poor solubility severely limits the research and application of carbon nanotubes. Chemical modification can not only effectively improve the solubility of carbon nanotubes, but also endow them with more functions and further broaden their application fields.

In recent years, the use of polymers for covalent chemical modification of carbon nanotubes has received extensive attention, and it has become a powerful means of preparing carbon nanotubes and their composite materials with certain specific functions. The material has great theoretical and practical significance. At present, many studies on the covalent modification of carbon nanotubes with polymers at home and abroad mainly focus on the synthesis of polymers, and there is no research report on the covalent modification of carbon nanotubes with cyclodextrin. However, synthetic polymers are mainly derived from increasingly depleted fossil resources, and some of the polymers used for modification also contain aromatic hydrocarbons such as toxic benzene rings (Feng, W.; Bai, X.D.; Lian, Y.Q.; et al. Carbon 2003, 41, 1551).

Cyclodextrin is a natural polymer derivative whose raw material is starch. From the early 1970s to the present, the research on cyclodextrins has entered a heyday. Due to the unrivaled and unique properties of many other macrocyclic compounds, such as crown ether, cryptand, calixarene, etc., cyclodextrin has become the preferred skeleton of supramolecular chemistry for the construction of various aggregates and complex superstructures . The chiral cavity in the cyclodextrin molecule has the characteristics of asymmetric induction, selective binding and catalysis of certain organic reactions, and can be used as a receptor to form inclusions with the help of intermolecular forces, changing the physical and chemical properties of the inclusion compounds. Properties (Gao Xiang, Zhang Yi, CN200610016993; Ren Yong, Gao Jianfeng, Yu Shuqin, etc., CN 200610041530; Ma Chengxiao, Cai Chunping, CN200610085742; Tong Linhui, Cyclodextrin Chemistry-Basics and Applications, Beijing, Science Press, 2001). The special structure of cyclodextrin enables it to recognize and selectively bind organic molecules or ions by virtue of differences in size, geometry, and properties. Therefore, it exhibits excellent performance in the analysis and separation of trace substances. Its application is almost Covers the entire field of chromatographic and electrophoretic separations and is used in the development of highly sensitive and specific detection sensors, for example, embedding lipophilic chain-modified β-cyclodextrin into lipophilic In a single layer, its sensitivity to detect the content of tetrachlorethylene in the air is as high as 100Hz/70ppm (CCLing, R. Darcy, J. Chem. Soc., Chem. Comm., 2, 203-205, 1993). In addition, cyclodextrins are also used in the development of liquid crystal materials, such as Darcy et al. using -SC _n H _2n+1 (n=2,4,10,16,18) groups to fully modify the primary group of β-cyclodextrin , to obtain tilted smectic liquid crystals (Tong Linhui, Cyclodextrin Chemistry-Basics and Applications, Beijing, Science Press, 2001). Recently, Jullien L. et al. established an energy transfer system for fully modifying the primary hydroxyl groups of β-cyclodextrin with naphthalene chromophores, which can transfer light energy to the merocyanines combined in the cavity, showing that the photosynthetic center Important potential (L. Jullien, J. Canceill, B. Valeur, et al, J. Am. Chem.l Soc., 118(23), 5432-5442, 1996). Therefore, cyclodextrins have broad application prospects in many aspects such as nano-functional materials, drug controlled release, micro-analysis, fine separation, supramolecular science and bio-functional simulation materials.

Compared with synthetic polymers, cyclodextrins are non-toxic, biocompatible, biodegradable, environmentally friendly, inexhaustible renewable resources, and are widely used in many fields. Since both carbon nanotubes and cyclodextrins are materials with many excellent properties, the new cyclodextrin-carbon nanotube derivatives are expected to be improved by combining cyclodextrin and carbon nanotubes through covalent bonds. In addition to the solubility of carbon nanotubes, in order to further develop new environmentally friendly nanocomposites that have both performances and even better performances, and have application prospects in the fields of separation analysis technology, supramolecular chemistry, catalysis, and environmental protection, we provide A base material.

Contents of the invention

The first object of the present invention is to provide a cyclodextrin-carbon nanotube derivative prepared from natural polymer materials-cyclodextrin and carbon nanotubes.

The second object of the present invention is to provide a preparation method of the above-mentioned cyclodextrin-carbon nanotube derivatives.

First purpose of the present invention is achieved through the following technical solutions:

A cyclodextrin-carbon nanotube derivative, which is based on the ball milling, purification and acidification of the original carbon nanotubes, and reacts with a halogenation reagent to convert the carboxylic acid groups on the surface of the carbon nanotubes into highly reactive After the acid halide group, it reacts with a binary functional organic compound to extend the active functional group from the surface of the carbon nanotube, and then reacts with trichloro-s-triazine to obtain an active chlorotriazine ring that can react with hydroxyl groups on the surface. The carbon nanotubes are finally prepared by nucleophilic substitution reaction with cyclodextrin. In the cyclodextrin-carbon nanotube derivative, the mass content ratio of cyclodextrin and carbon nanotube is about 0.1-0.8:1.

Second object of the present invention is achieved through the following technical solutions:

A preparation method of cyclodextrin-carbon nanotube derivatives, which comprises the following steps:

1. Stir the carbon nanotubes and the halogenation reagent in the organic solvent A evenly, then ultrasonically and centrifuge, wash them with the organic solvent B, and dry them in vacuum at room temperature to obtain carbon nanotubes with acid halide functional groups on the surface;

2. Mix the above-mentioned carbon nanotubes with acid halide functional groups, organic compounds with binary functional groups and deacidification agent in organic solvent C, stir evenly, then fully ultrasonically react under the protection of nitrogen, evaporate organic solvent C and deacidification agent, and then washed with the mixed solvent D, and vacuum-dried at room temperature to obtain derivatives with active functional groups extending from the surface of carbon nanotubes;

3. Mix the above-mentioned carbon nanotubes with active functional groups and trichloro-s-triazine in tetrahydrofuran, stir evenly, after ultrasonication at low temperature, fully react at low temperature, wash with organic solvent E, and then Vacuum drying to obtain carbon nanotube derivatives with active chlorotriazine-containing rings on the surface;

4. After dissolving the above-mentioned carbon nanotube derivatives with active chlorotriazine rings in N, N'-dimethylformamide, add them to N, N'-dimethylformamide dissolved in cyclodextrin In the amide solution, stir at 15-25°C for 1-5h, in a 100kHz, 200W ultrasonic instrument at 15-25°C for 1-12h, heat up to 35-50°C under the protection of nitrogen and react at a constant temperature for 12-48h , and then heated to 85-100°C for constant temperature reaction for 24-72h, distilled off N,N'-dimethylformamide; added 200-500ml of distilled water at 90°C, ultrasonicated for 0.5-1h, and pumped through a 0.8μm nylon microporous filter membrane filter, and rinse the filter cake with 500ml 90°C distilled water; transfer the filter cake into a 2L beaker, add 500-1500ml of 90°C distilled water, after ultrasonication for 0.5-2h, stir at room temperature for 1-2h, and then pass through a 0.8μm nylon microporous filter Membrane suction filtration, and rinse the filter cake with 500ml 90°C distilled water, repeat the operation 15-30 times; wrap the filter cake in qualitative filter paper, use distilled water as solvent, extract with Soxhlet extractor for 48-72h, at 30°C The product was obtained after drying under vacuum for 24-72h.

The carbon nanotube in the above step 1 is 1-30g, the halogenation reagent is 1-200g; the organic solvent is 100-2000ml; the stirring conditions are: temperature 30-50°C, time 1-12h; the ultrasonic conditions are: at 100kHz, 200W Sonicate in an ultrasonic instrument at 30-80°C for 48-72h; the centrifugation condition is: centrifuge at a speed of 3000-5000rpm for 10-60min; the condition of vacuum drying is: vacuum dry at 20-40°C for 24-56h.

The halogenation reagent in the above step 1 is one of phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide or thionyl chloride.

The organic solvent A in the above step 1 is acetone, tetrahydrofuran, benzene, toluene, xylene, dimethyl sulfoxide, N-methylpyrrolidone, N, N'-dimethylformamide or N, N'-dimethyl One or more of acetamides.

The organic solvent B in the above step 1 is one of acetone, ether, carbon tetrachloride or tetrahydrofuran.

The carbon nanotube in the above step 2 is 0.1-20g; the binary functional group organic compound is 5-150g; the deacidification agent is 1-50ml; the organic solvent is 100-1500ml; the stirring condition is to stir at 30-60°C for 1- 12h; ultrasonic condition is 100kHz, 200W ultrasonic instrument at 30-90℃ for 12-48h; the condition of mixed solvent D washing is: add mixed solvent D 200-500ml, ultrasonic 0.5-1h, and then pass through 0.8μm Suction filter with nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D; transfer the filter cake into a 2L beaker, add 500-1500ml of mixed solvent D, after ultrasonication for 0.5-2h, stir at room temperature for 1-2h, and then pass through 0.8 Suction filter with μm nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D, repeat this operation 10-20 times; the condition of vacuum drying is vacuum drying at 10-30°C for 24-72h.

The active organic compound of binary functional group in the above step 2 is ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- One of hexanediol, diethylene glycol, ethylenediamine, 1,3-propylenediamine and 1,6-hexanediamine.

The deacidification agent in the above step 2 is one or both of triethylamine, pyridine, 3-picoline and lutidine.

The organic solvent C in the above step 2 is acetone, tetrahydrofuran, carbon tetrachloride, benzene, toluene, xylene, dimethyl sulfoxide, N-methylpyrrolidone, N, N'-dimethylformamide or N, N One or more of '-dimethylacetamide.

The mixed solvent D in the above step 2 consists of acetone, ethanol and distilled water, wherein the volume ratio of acetone, ethanol and distilled water is 2:3:5.

The carbon nanotube in the above step 3 is 0.1-18g; the trichloro-s-triazine is 1-120g; the tetrahydrofuran is 50-1200ml; the stirring condition is 0-10°C for 12-24h; the ultrasonic condition is 100kHz, 200W Ultrasound at 0-10°C for 1-12h in a special ultrasonic instrument; the reaction condition is to react at 0-10°C for 24-72h; the conditions for cleaning with organic solvent E are: add 200-500ml of organic solvent E, ultrasonic 0.5-1h, Then filter through a 0.8μm polytetrafluoroethylene microporous membrane, and rinse the filter cake with 500ml of organic solvent E; transfer the filter cake into a 2L beaker, add 500-1000ml of organic solvent E, ultrasonic 0.5-2h, and stir at room temperature 1-2h, and then filter through a 0.8μm polytetrafluoroethylene microporous membrane, and rinse the filter cake with 500ml of organic solvent E, and repeat this operation 10-25 times; the condition of vacuum drying is vacuum at 10-15℃ Dry for 24-48h.

The organic solvent E in the above step 3 is one of acetone or tetrahydrofuran.

The carbon nanotubes in the above step 4 are 0.1-15g; the N,N'-dimethylformamide for dissolving the carbon nanotubes is 50-500ml; the cyclodextrin is 1-80g; the N,N' for dissolving the cyclodextrin -Dimethylformamide is 50-1000ml.

The cyclodextrin in step 4 above is α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydroxypropyl-γ-cyclodextrin or acetylcyclodextrin dextrin.

Add a pretreatment step to carbon nanotubes before the above step 1: put 15 stainless steel balls with a diameter of 6-8mm and 25 g of unpurified carbon nanotubes in two identical 200ml nylon tanks, and then drop them separately Add 10ml of absolute ethanol and seal it with a nylon cap. Two ball mill jars were symmetrically put into a planetary ball mill (QM-BP type, manufactured by Nanjing University), and ball milled for 56 hours under the condition that the rotation speed was 350 rpm and the rotation direction was automatically switched every 30 minutes. Then soak and reflux with 30-50wt% hydrofluoric acid aqueous solution for 24h, filter, wash with running water, and dry; ultrasonically 24h in 2M _HNO solution, reflux for 24h, filter, and wash with running water; -10, ultrasonicated in 20-40wt% OP-10 aqueous solution for 5 hours, filtered, washed with running water, repeated 2-3 times, immersed in 3M HCl solution, ultrasonicated for 12-24 hours, filtered, washed with running water Clean and dry; finally, after ultrasonication for 72-96 hours in concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 0.5:1-9.5:1, reflux for 72-96 hours, centrifuge, wash with running water, and dry. The above treatment process produces carboxyl functional groups on the surface of the carbon nanotubes while purifying them.

Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

The cyclodextrin-carbon nanotube derivatives provided by the present invention are environmentally friendly, and can be used in dimethyl sulfoxide, N-methylpyrrolidone, N, N'-dimethylformamide and N, N'-dimethylacetamide It has good solubility in organic solvents. The preparation conditions of the derivative are easy to meet, and the source of raw materials is abundant, and the cost is low.

The invention establishes a method for preparing cyclodextrin-carbon nanotube derivatives by using carbon nanotubes and natural polymer cyclodextrin as raw materials. The test results show that the chemical structure of the derivative is stable. It not only has good solubility, dispersibility and stability in various organic solvents, but also has many excellent properties of carbon nanotubes and cyclodextrins. It is a kind of As an environmentally friendly material, its value can be expected in the fields of separation analysis technology, supramolecular chemistry, catalytic materials, and environmental protection materials. The invention has high scientific and technological content, is innovative, and has good application prospects.

Detailed ways

The present invention prepares a new type of derivative with carbon nanotubes and cyclodextrin as raw materials for the first time. The technical scheme of the present invention is further described below in conjunction with specific embodiment:

Example 1

A β-cyclodextrin-carbon nanotube derivative with a mass content ratio of cyclodextrin and carbon nanotube of about 0.8:1, which is based on ball milling, purification and acidification of the original carbon nanotube, and halogenated Reagent reaction, the carboxylic acid group on the surface of the carbon nanotube is converted into a highly reactive acid halide group, and then reacted with a binary functional organic compound to extend the active functional group from the surface of the carbon nanotube, and then react with the trichloro s-triazine reaction to obtain carbon nanotubes with active chlorotriazine rings on the surface that can react with hydroxyl groups, and finally prepare them through nucleophilic substitution reaction with β-cyclodextrin. The specific preparation method is as follows:

The carbon nanotubes were first pretreated according to the following steps: 15 stainless steel balls with a diameter of 6-8mm and 25g of unpurified carbon nanotubes were placed in two identical 200ml nylon tanks, and then 10ml of non-purified carbon nanotubes were added dropwise. hydroethanol, and seal with a nylon cap. Two ball mill jars were symmetrically put into a planetary ball mill (QM-BP type, manufactured by Nanjing University), and ball milled for 56 hours under the condition that the rotation speed was 350 rpm and the rotation direction was automatically switched every 30 minutes. Then soak and reflux with 30-50wt% hydrofluoric acid aqueous solution for 24h, filter, wash with running water, and dry; ultrasonically 24h in 2M _HNO solution, reflux for 24h, filter, and wash with running water; -10, ultrasonicated in 20-40wt% OP-10 aqueous solution for 5 hours, filtered, washed with running water, repeated 2-3 times, immersed in 3M HCl solution, ultrasonicated for 12-24 hours, filtered, washed with running water Clean and dry; finally, after ultrasonication for 72-96 hours in concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 0.5:1-9.5:1, reflux for 72-96 hours, centrifuge, wash with running water, and dry. The above treatment process produces carboxyl functional groups on the surface of the carbon nanotubes while purifying them.

Then take 28g of pretreated carbon nanotubes and add them to 1850ml N-methylpyrrolidone dissolved with 180g of phosphorus trichloride, stir at 40°C for 12h, and after ultrasonic reaction at 70°C for 72h, centrifuge at 4500rpm for 60min , washed with diethyl ether, and vacuum-dried at 30° C. for 48 hours to obtain carbon nanotubes with acid halide functional groups on the surface.

Take 20g of the above-mentioned carbon nanotubes with acid halide functional groups on the surface, add them to 1500ml N,N'-dimethylacetamide containing 150g 1,3-propanediol and 50ml pyridine, stir at 60°C for 12h, After ultrasonic reaction for 48 hours, distill off N,N'-dimethylacetamide and pyridine, add 500ml of mixed solvent D, ultrasonicate for 1h, and then filter through 0.8μm nylon microporous membrane, and use 500ml volume ratio of 2:3 : 5 mixed solvent D of acetone, ethanol and distilled water to rinse the filter cake; transfer the filter cake to a 2L beaker, add 1500ml of mixed solvent D, after ultrasonication for 2h, stir at room temperature for 1.5h, and then pass through a 0.8μm nylon microporous filter membrane Suction filtration, and rinse the filter cake with 500ml of mixed solvent D, repeat the operation 20 times, and finally vacuum-dry at 30°C for 72 hours to obtain derivatives with hydroxyl groups extending from the surface of carbon nanotubes—carbon nanotubes with hydroxyl groups on the surface. Tube Derivatives.

Then take 18g of the above-mentioned carbon nanotube derivatives with hydroxyl groups on the surface, add them into 1200ml tetrahydrofuran containing 120g of trichloro-s-triazine, stir at 10°C for 24h, ultrasonicate at 10°C for 12h, and then react at 10°C 72h, add 500ml tetrahydrofuran, sonicate for 1h, then filter through a 0.8μm polytetrafluoroethylene microporous membrane, and wash the filter cake with 500ml tetrahydrofuran; Stir for 2 hours, then suction filter through a 0.8 μm polytetrafluoroethylene microporous filter membrane, and rinse the filter cake with 500ml tetrahydrofuran, repeat this operation 20 times, and finally dry it in vacuum at 10°C for 48 hours to obtain active chlorotriazines on the surface. ring carbon nanotube derivatives.

Take 15g of the above-mentioned carbon nanotube derivatives with active chlorotriazine rings, dissolve them in 500ml N,N'-dimethylformamide, and add them to 1000ml N,N'- In dimethylformamide solution, stir at 15°C for 5h, sonicate at 15°C in a 100kHz, 200W ultrasonic instrument for 12h, heat up to 50°C for 48h under the protection of nitrogen, and then raise the temperature to 100°C for constant temperature reaction After 72 hours, evaporate N,N'-dimethylformamide; add 500ml of 90°C distilled water, ultrasonicate for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of 90°C distilled water; transfer the filter cake to Put it into a 2L beaker, add 1500ml of distilled water at 90°C, after ultrasonication for 2h, stir at room temperature for 2h, then filter through a 0.8μm nylon microporous membrane, and wash the filter cake with 500ml of distilled water at 90°C, repeat the operation 30 times; The cake was wrapped in qualitative filter paper, extracted with distilled water for 72 hours with a Soxhlet extractor, and vacuum-dried at 30°C for 72 hours to obtain a β-cyclodextrin-carbon nanotube derivative product.

Example 2

A cyclodextrin-carbon nanotube derivative whose mass content ratio of cyclodextrin and carbon nanotube is about 0.5:1, and its specific preparation method is as follows:

The carbon nanotubes are firstly pretreated, and the pretreatment method is the same as that of the above-mentioned embodiment 1.

Then take 16 g of the pretreated carbon nanotubes and add them to 1000 ml of acetone dissolved with 100 g of phosphorus tribromide, stir at 45 ° C for 6 h, and after ultrasonic reaction at 75 ° C for 56 h, centrifuge at a speed of 5000 rpm for 35 min, wash with ether After cleaning, vacuum-dry at 20° C. for 56 hours to obtain carbon nanotubes with acid halide functional groups on the surface.

Take 10g of the above-mentioned carbon nanotubes with acid halide functional groups on the surface, add them to 700ml of N-methylpyrrolidone containing 75g of 1,3-propylenediamine and 25ml of triethylamine, stir at 30°C for 6h, After ultrasonic reaction for 36 hours, distill off N-methylpyrrolidone and triethylamine, add 200ml of mixed solvent D of acetone, ethanol and distilled water with a volume ratio of 2:3:5, ultrasonicate for 0.5h, and then pass through a 0.8μm nylon microporous filter Membrane suction filtration, and rinse the filter cake with 500ml of mixed solvent D; transfer the filter cake into a 2L beaker, add 750ml of mixed solvent D, after ultrasonication for 1h, stir at room temperature for 1.5h, and then filter through a 0.8μm nylon microporous membrane , and rinse the filter cake with 500ml of mixed solvent D, and repeat the operation 16 times, and finally dry it in vacuum at 10°C for 60 hours to obtain a derivative with amino groups extending from the surface of carbon nanotubes—a derivative of carbon nanotubes with amino groups on the surface thing.

Then take 9g of the above-mentioned carbon nanotube derivatives with amino groups on the surface, add them into 600ml tetrahydrofuran containing 60g of trichloro-s-triazine, stir at 5°C for 12h, ultrasonicate at 5°C for 6h, and react at 0°C 32h, add 250ml of acetone, sonicate for 0.5h, then filter through a 0.8μm polytetrafluoroethylene microporous membrane, and rinse the filter cake with 500ml of acetone; transfer the filter cake into a 2L beaker, add 750ml of acetone, and sonicate for 1h, Stir at room temperature for 1 hour, then filter through a 0.8 μm polytetrafluoroethylene microporous filter membrane, and rinse the filter cake with 500 ml of acetone. Carbon nanotube derivatives of oxazine rings.

Take 8g of the above-mentioned carbon nanotube derivatives with active chlorotriazine rings, dissolve them in 300ml N,N'-dimethylformamide, and add them to 500ml N,N'-dimethyformamide dissolved in 40gα-cyclodextrin. In methylformamide solution, stir at 25°C for 3h, in a 100kHz, 200W ultrasonic instrument at 25°C for 6h, heat up to 35°C and react at a constant temperature for 24h under the protection of nitrogen, then raise the temperature to 85°C for 56h , evaporate N,N'-dimethylformamide; add 350ml of 90°C distilled water, ultrasonicate for 0.5h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of 90°C distilled water; transfer the filter cake to Put it into a 2L beaker, add 1000ml of 90°C distilled water, after ultrasonication for 1h, stir at room temperature for 1.5h, then filter through a 0.8μm nylon microporous membrane, and wash the filter cake with 500ml of 90°C distilled water, repeat the operation 20 times; The filter cake was wrapped in qualitative filter paper, extracted with distilled water for 56 hours with a Soxhlet extractor, and vacuum-dried at 30°C for 48 hours to obtain the α-cyclodextrin-carbon nanotube derivative product.

Example 3

A cyclodextrin-carbon nanotube derivative whose mass content ratio of cyclodextrin and carbon nanotube is about 0.1:1, and its specific preparation method is as follows:

The carbon nanotubes are firstly pretreated, and the pretreatment method is the same as that of the above-mentioned embodiment 1.

Then take 1 g of the pretreated carbon nanotubes and add them to 100 ml of toluene dissolved with 1 g of thionyl chloride, stir at 30 ° C for 1 h, and after ultrasonic reaction at 30 ° C for 48 h, centrifuge at a speed of 3000 rpm for 10 min. After carbonization cleaning, vacuum drying at 40° C. for 24 h to obtain carbon nanotubes with acid halide functional groups on the surface.

Take 0.1 g of the above-mentioned carbon nanotubes with acid halide functional groups on the surface, add them to 100 ml of tetrahydrofuran containing 5 g of diethylene glycol and 1 ml of lutidine, stir at 45 ° C for 1 h, and ultrasonically react at 30 ° C for 12 h , distill off tetrahydrofuran and lutidine, add 350ml of acetone, ethanol and distilled water mixed solvent D with a volume ratio of 2:3:5, sonicate for 0.8h, then filter through a 0.8μm nylon microporous membrane, and use 500ml of mixed solvent Rinse the filter cake with D; transfer the filter cake into a 2L beaker, add 1500ml of mixed solvent D, after ultrasonication for 0.5h, stir at room temperature for 1.5h, then filter through a 0.8μm nylon microporous membrane, and moisten with 500ml of mixed solvent D Wash the filter cake, and repeat this operation 16 times, and finally vacuum-dry at 10° C. for 60 hours to obtain a derivative with amino groups extending from the surface of carbon nanotubes—a carbon nanotube derivative with amino groups on the surface.

Then take 0.1 g of the above-mentioned carbon nanotube derivatives with amino groups on the surface, add them to 50 ml of tetrahydrofuran containing 1 g of trichloro-s-triazine, stir at 0 ° C for 16 h, ultrasonicate at 0 ° C for 1 h, and then React for 24 hours, add 200ml of acetone, sonicate for 0.5h, then filter through a 0.8μm polytetrafluoroethylene microporous membrane, and rinse the filter cake with 500ml of acetone; transfer the filter cake to a 2L beaker, add 750ml of acetone, and sonicate for 1h , stirred at room temperature for 1 h, then filtered through a 0.8 μm polytetrafluoroethylene microporous membrane, and rinsed the filter cake with 500 ml of acetone. Carbon nanotube derivatives of triazine rings.

Take 0.1g of the above-mentioned carbon nanotube derivative with active chlorotriazine ring, dissolve it in 50ml N,N'-dimethylformamide, add it to 50ml N,N'-dimethylformamide dissolved with 1g acetyl cyclodextrin In the '-dimethylformamide solution, stir at 20°C for 1h, sonicate in a 100kHz, 200W ultrasonic instrument at 20°C for 1h, raise the temperature to 40°C under nitrogen protection, and react at a constant temperature for 12h, then raise the temperature to 90°C React at constant temperature for 24 hours, distill off N,N'-dimethylformamide; add 200ml of 90°C distilled water, ultrasonicate for 0.8h, then filter through a 0.8μm nylon microporous membrane, and wash the filter cake with 500ml of 90°C distilled water; Transfer the filter cake into a 2L beaker, add 500ml of 90°C distilled water, ultrasonicate for 0.5h, stir at room temperature for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of 90°C distilled water, repeat the operation for 10 Second; wrap the filter cake in qualitative filter paper, use distilled water as the solvent, extract with a Soxhlet extractor for 48 hours, and dry it in vacuum at 30°C for 24 hours to obtain the acetyl cyclodextrin-carbon nanotube derivative product.

The present invention is not limited to the above implementation manners, as long as the schemes mentioned in this specification can be implemented.

Claims (2)

1. A cyclodextrin-carbon nanotube derivative is characterized in that: it is on the basis of ball milling, purification and acidification treatment of the original carbon nanotube, reacts with a halogenation reagent, and the carboxylic acid group on the surface of the carbon nanotube After being converted into an acid halide group with strong reactivity, it reacts with a binary functional group organic compound to extend the active functional group from the surface of the carbon nanotube, and then reacts with trichloro-s-triazine to obtain a surface that can react with a hydroxyl group. Active carbon nanotubes containing chlorotriazine rings are finally prepared by nucleophilic substitution reaction with cyclodextrin, and the binary functional group organic compounds are ethylene glycol, 1,3-propanediol, 1,3-butanediol Alcohol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, ethylenediamine, 1,3-propylenediamine and 1,6-hexanediol A kind of diamine; in the cyclodextrin-carbon nanotube derivative, the mass content ratio of cyclodextrin and carbon nanotube is 0.1-0.8:1. 2. A preparation method of cyclodextrin-carbon nanotube derivatives, comprising the following steps: Pretreatment steps of carbon nanotubes: 15 stainless steel balls with a diameter of 6-8mm and 25g of unpurified carbon nanotubes are respectively loaded into two identical 200ml ball mill jars, and then 10ml of absolute ethanol is added dropwise respectively, And seal it with a nylon cover; put two ball mill jars symmetrically into the planetary ball mill, and ball mill for 56 hours at a speed of 350rpm, and automatically change the direction of rotation every 30 minutes; then soak in 30-50wt% hydrofluoric acid aqueous solution After reflux for 24 hours, filter, wash with running water, and dry; ultrasonically in 2M HNO ₃ solution for 24 hours, reflux for 24 hours, filter, wash with running water; Ultrasound in aqueous solution of 10 for 5 hours, filter, wash with running water, repeat 2-3 times, immerse in 3M HCl solution, sonicate for 12-24 hours, filter, wash with running water, and dry; finally, the volume ratio is 0.5:1 - 9.5: 1 concentrated sulfuric acid and concentrated nitric acid, after ultrasonication for 72-96h, reflux for 72-96h, centrifuge, wash with running water, and dry; the above treatment process produces carboxyl functional groups on the surface while purifying carbon nanotubes; Then proceed as follows: 1) Stir the carbon nanotubes and the halogenation reagent in the organic solvent A evenly, then ultrasonically and centrifuge, wash with the organic solvent B, and dry in vacuum at 20-40°C to obtain carbon nanotubes with acid halide functional groups on the surface ; 2) Mix the above-mentioned carbon nanotubes with acyl halide functional group, binary functional organic compound and deacidification agent in organic solvent C, stir evenly, then fully ultrasonically react under nitrogen protection, evaporate organic solvent C and deacidification agent, and then washed with the mixed solvent D, and vacuum-dried at 10-30°C to obtain derivatives with active functional groups extending from the surface of carbon nanotubes; 3) Mix the above-mentioned carbon nanotubes with active functional groups and trichloro-s-triazine in tetrahydrofuran, stir evenly, after ultrasonication at 0-10°C, fully react at 0-10°C, wash with organic solvent E After cleaning, vacuum-dry at 10-15°C to obtain a carbon nanotube derivative with active chlorotriazine-containing rings on the surface; 4) After dissolving the above-mentioned carbon nanotube derivatives with active chlorotriazine rings in N, N'-dimethylformamide, add them to N, N'-dimethylformamide dissolved in cyclodextrin In the amide solution, stir at 15-25°C for 1-5h, in a 100kHz, 200W ultrasonic instrument at 15-25°C for 1-12h, heat up to 35-50°C under the protection of nitrogen and react at a constant temperature for 12-48h , and then heated to 85-100°C constant temperature reaction for 24-72h, distilled off the solvent; add 200-500ml of 90°C distilled water, ultrasonic 0.5-1h, then filter through 0.8μm nylon microporous membrane, and rinse with 500ml of 90°C distilled water Filter cake: transfer the filter cake into a 2L beaker, add 500-1500ml of 90°C distilled water, ultrasonicate for 0.5-2h, stir at room temperature for 1-2h, then filter through a 0.8μm nylon microporous membrane, and use 500ml of 90°C distilled water Rinse the filter cake, and repeat this operation 15-30 times; wrap the filter cake in qualitative filter paper, use distilled water as solvent, extract with a Soxhlet extractor for 48-72 hours, and vacuum dry at 30°C for 24-72 hours to obtain the product ; The halogenating reagent in the step 1) is one of phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide or thionyl chloride; the organic solvent A is acetone, tetrahydrofuran, benzene, toluene, di One or more of toluene, dimethyl sulfoxide, N-methylpyrrolidone, N, N'-dimethylformamide or N, N'-dimethylacetamide; the organic solvent B is acetone, One of ether, carbon tetrachloride or tetrahydrofuran; the binary functional organic compound in the step 2) is ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol Alcohol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, ethylenediamine, 1,3-propylenediamine and 1,6-hexanediamine; The deacidifying agent is one or both of triethylamine, pyridine, 3-picoline and lutidine; the organic solvent C is acetone, tetrahydrofuran, carbon tetrachloride, benzene, toluene, One or more of toluene, dimethyl sulfoxide, N-methylpyrrolidone, N, N'-dimethylformamide or N, N'-dimethylacetamide; the mixed solvent D consists of acetone, Composed of ethanol and distilled water, wherein the volume ratio of acetone, ethanol and distilled water is 2:3:5; the organic solvent E in the step 3) is one of acetone or tetrahydrofuran; the cyclodextrin in the step 4) is alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl-beta-cyclodextrin, hydroxypropyl-gamma-cyclodextrin or acetylcyclodextrin; The carbon nanotube in the step 1) is 1-30g, the halogenation reagent is 1-200g; the organic solvent A is 100-2000ml; the stirring conditions are: temperature 30-50°C, time 1-12h; the ultrasonic conditions are: at Ultrasonic at 30-80°C for 48-72h in a 100kHz, 200W ultrasonic instrument; centrifugation conditions: centrifuge at a speed of 3000-5000rpm for 10-60min; vacuum drying conditions: vacuum dry at 20-40°C for 24-56h ; The carbon nanotube in the step 2) is 0.1-20g; the binary functional group organic compound is 5-150g; the deacidification agent is 1-50ml; the organic solvent C is 100-1500ml; the stirring condition is at 30-60°C Stir for 1-12h; ultrasonic conditions are 100kHz, 200W ultrasonic instrument at 30-90°C for 12-48h; wash the mixed solvent D conditions: add mixed solvent D 200-500ml, ultrasonic 0.5-1h, and then Suction filter through a 0.8 μm nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D; transfer the filter cake into a 2L beaker, add 500-1500ml of mixed solvent D, ultrasonicate for 0.5-2h, and stir at room temperature for 1-2h. Then filter through a 0.8 μm nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D, and repeat this operation 10-20 times; the vacuum drying condition is to dry at 10-30°C for 24-72h; The carbon nanotube in the step 3) is 0.1-18g; the trichloro-s-triazine is 1-120g; the tetrahydrofuran is 50-1200ml; the stirring condition is 12-24h at 0-10°C; the ultrasonic condition is 100kHz , Ultrasound at 0-10°C for 1-12h in a 200W ultrasonic instrument; the reaction condition is to react at 0-10°C for 24-72h; the conditions for cleaning with organic solvent E are: add organic solvent E 200-500ml, ultrasonic 0.5 -1h, then filter through a 0.8μm polytetrafluoroethylene microporous membrane, and rinse the filter cake with 500ml of organic solvent E; transfer the filter cake to a 2L beaker, add 500-1000ml of organic solvent E, and sonicate for 0.5-2h , stirred at room temperature for 1-2h, then filtered through a 0.8μm polytetrafluoroethylene microporous membrane, and rinsed the filter cake with 500ml of organic solvent E, and repeated the operation 10-25 times; the condition of vacuum drying is 10-15 Vacuum dry at ℃ for 24-48h; The carbon nanotube in the step 4) is 0.1-15g; the N,N'-dimethylformamide that dissolves the carbon nanotube is 50-500ml; the cyclodextrin is 1-80g; the N that dissolves the cyclodextrin, N'-dimethylformamide is 50-1000ml.