CN101239715B - A kind of cellulose diacetate-carbon nanotube derivative and its preparation method and application - Google Patents

Abstract

The invention discloses a cellulose diacetate-carbon nanotube derivative, which is based on the ball milling, purification and acidification treatment of the original carbon nanotube, and reacts with a halogenation reagent to transform the carboxylic acid group on the surface of the carbon nanotube After being an acyl 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 reactive group on the surface that can react with hydroxyl groups. Carbon nanotubes containing chlorotriazine rings are finally prepared by nucleophilic substitution reaction with cellulose diacetate, and in the derivatives, the mass content ratio of cellulose diacetate and carbon nanotubes is about 0.6-8:1. The invention also discloses the preparation method and application of the derivative. The derivatives of the invention are environmentally friendly and have good solubility. The preparation conditions of the derivative are easy to meet, and the source of raw materials is abundant, and the cost is low, so it can be expected to have high value in the field of tobacco filter materials and the like.

Description

A kind of cellulose diacetate-carbon nanotube derivative and its preparation method and application

technical field

The invention relates to a derivative, in particular to a cellulose diacetate-carbon nanotube derivative, a preparation method and an application of the derivative, and belongs to the field of natural polymers and also belongs to the field of nanomaterials.

Background technique

In 1991, Japanese scientist Iijima S. discovered carbon nanotubes (Iijima 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, further broadening 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 cellulose acetate, a natural polymer derivative. 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).

Cellulose acetate, discovered in 1869, is one of the earliest researched and produced cellulose derivatives, and is also recognized as a vital organic acid ester of cellulose; among them, cellulose diacetate with a degree of esterification of 2-3 is soluble Based on acetone, it has been widely used in the manufacture of cigarette filter tow, high-performance separation membrane materials, textile materials, coatings, plastics, etc. (Gao Jie, Tang Liegui. Cellulose Science. Beijing: Science Press, 1996; Xu Dongsheng. Cellulose Derivatives . Beijing: Chemical Industry Press, 2001).

Compared with synthetic polymers, cellulose diacetate is a non-toxic, biocompatible, biodegradable, environmentally friendly, inexhaustible renewable resource, and is widely used in many fields. Therefore, cellulose diacetate can be used as an ideal polymer for covalently modifying carbon nanotubes. Since both carbon nanotubes and cellulose diacetate are materials with many excellent properties, combining cellulose diacetate and carbon nanotubes through covalent bonds is expected to improve the solubility of carbon nanotubes and develop a combination It is a green and environmentally friendly new nanocomposite material with or even better than the performance of the two, and has application prospects in fields such as cigarette filter materials.

Contents of the invention

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

The second object of the present invention is to provide a method for preparing the above-mentioned cellulose diacetate-carbon nanotube derivatives.

The third object of the present invention is to provide the use of the above-mentioned cellulose diacetate-carbon nanotube derivatives.

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

A cellulose diacetate-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 more reactive carbon nanotubes. After a strong acid halide group, react with a binary functional group organic compound to extend the active functional group from the surface of the carbon nanotube, and then react with trichloro-s-triazine to obtain an active chlorotriazine that can react with hydroxyl groups on the surface Ring carbon nanotubes are finally prepared by nucleophilic substitution reaction with cellulose diacetate. In the cellulose diacetate-carbon nanotube derivative, the mass content ratio of cellulose diacetate and carbon nanotube is about 0.6-8:1.

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

A kind of preparation method of cellulose diacetate-carbon nanotube derivative, it comprises the following steps:

1. Pretreatment of carbon nanotubes;

2. Stir the pretreated carbon nanotubes and halogenation reagents evenly in organic solvent A, then ultrasonically and centrifuge, and after being washed with organic solvent B, vacuum-dry at room temperature to obtain carbon nanotubes with acid halide functional groups on the surface. Tube;

3. Mix the above-mentioned carbon nanotubes with acyl 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;

4. 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 Vacuum drying to obtain carbon nanotube derivatives with active chlorotriazine-containing rings on the surface;

5. After dissolving the above-mentioned carbon nanotube derivatives with active chlorotriazine-containing rings in the organic solvent F, add them to the acetone solution in which cellulose diacetate is dissolved, and stir at 15-25°C for 1-5h, Ultrasound at 15-25°C for 1-12h in a 100kHz, 200W ultrasonic instrument, and then heated to 35-50°C for 12-48h under the protection of nitrogen, then heated to 85-100°C for 24-72h, evaporated Remove organic solvent F and acetone; add 200-500ml of acetone, sonicate for 0.5-1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of acetone; transfer the filter cake to a 2L beaker, add 500ml of acetone -1500ml, after ultrasonication for 0.5-2h, stir at room temperature for 1-2h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml acetone, repeat this operation 10-20 times; wrap the filter cake in a qualitative In filter paper, use acetone as solvent, extract with Soxhlet extractor for 48-72h, and dry in vacuum at 30°C for 24-72h to obtain the product.

The carbon nanotube in the above step 2 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 2 is one of phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide or thionyl chloride.

The organic solvent A in the above step 2 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 2 is one of acetone, ether, carbon tetrachloride or tetrahydrofuran.

The carbon nanotube in the above step 3 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 0.8μm Suction filter with a nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D, and 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-mentioned step 3 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 3 is one or both of triethylamine, pyridine, 3-picoline and lutidine.

The organic solvent C in the above step 3 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 3 is composed 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 4 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 4 is one of acetone or tetrahydrofuran.

The amount of carbon nanotubes in the above step 5 is 0.1-15g; the organic solvent F for dissolving carbon nanotubes is 50-400ml; the amount of cellulose diacetate is 1-30g; the amount of acetone is 50-250ml.

The viscosity-average molecular weight of the cellulose diacetate in the above step 5 is 1000-50000, and the degree of esterification is 2-3.

The organic solvent F in the above step 5 is one of dimethyl sulfoxide, N-methylpyrrolidone, N, N'-dimethylformamide or N, N'-dimethylacetamide.

The pretreatment of carbon nanotubes in said step 1 is carried out through the following steps: 15 stainless steel balls with a diameter of 6-8mm and 25g of unpurified carbon nanotubes are respectively loaded in two identical 200ml nylon tanks, and then respectively Add 10ml of absolute ethanol dropwise 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.

The third purpose of the present invention is achieved through the following solutions:

Application of a cellulose diacetate-carbon nanotube derivative of the present invention in filter materials for cigarettes. Taking the cellulose diacetate-carbon nanotube derivatives whose mass content ratio of cellulose diacetate and carbon nanotubes is 1.9:1 as an example, according to the "Industrial Standards of the People's Republic of China (Cigarettes): Determination of total Particulate matter and tar (industry standard), 1996 ", with a kind of cigarette filter tip (Little Panda brand, Guangzhou Cigarette Factory) as reference object, under the same quality and the same test condition, the filter tip containing the derivative ( The mass content of the derivative is 25%), and the removal ability of nicotine and tar is respectively increased by 31% and 26% compared with the former.

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

The cellulose diacetate-carbon nanotube derivatives provided by the present invention are environmentally friendly, can be dissolved in a small amount in acetone, and can be dissolved in dimethyl sulfoxide, N-methylpyrrolidone, N, N'-dimethylformamide and N, It has good solubility in organic solvents such as N'-dimethylacetamide. 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 cellulose diacetate-carbon nanotube derivatives by using carbon nanotubes and natural polymer cellulose diacetate 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 cellulose diacetate. It is an environmentally friendly material, and its value in fields such as cigarette filter materials can be expected. The invention has high scientific and technological content, is innovative, and has good application prospects.

Detailed ways

The present invention prepares a novel derivative for the first time by using carbon nanotubes and cellulose diacetate as raw materials. The technical scheme of the present invention is further described below in conjunction with specific embodiment:

Example 1

A cellulose diacetate-carbon nanotube derivative with a mass content ratio of cellulose diacetate and carbon nanotubes of about 3.2:1. 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 active carbon nanotubes containing chlorotriazine rings that can react with hydroxyl groups on the surface, and finally prepare them through nucleophilic substitution reaction with cellulose diacetate. 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. water to ethanol, 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 20 g of pretreated carbon nanotubes and add them to 1000 ml of N-methylpyrrolidone dissolved with 100 g of phosphorus trichloride, stir at 40 °C for 10 h, and ultrasonically react at 75 °C for 72 h, then centrifuge at 4000 rpm for 60 min , washed with ether, and dried in vacuum at 20° C. for 48 hours to obtain carbon nanotubes with acid halide functional groups on the surface.

Take 15g of the above-mentioned carbon nanotubes with acid halide functional groups on the surface, add them to 600ml of N,N'-dimethylacetamide containing 50g of 1,3-propanediol and 25ml of pyridine, stir at 60°C for 10h, After ultrasonic reaction for 48 hours, evaporate N,N'-dimethylacetamide and pyridine, add 300ml of mixed solvent D, ultrasonicate for 0.5h, then filter through 0.8μm nylon microporous membrane, and rinse with 500ml of mixed solvent D Filter cake: transfer the filter cake into a 2L beaker, add 800ml of mixed solvent D, after ultrasonication for 0.5h, stir at room temperature for 2h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D, This operation was repeated 10 times, and finally vacuum-dried at 30° C. for 48 hours to obtain derivatives with hydroxyl groups extending from the surface of carbon nanotubes—carbon nanotube derivatives with hydroxyl groups on the surface.

Then take 10 g of the above-mentioned carbon nanotube derivatives with hydroxyl groups on the surface, add them to 700 ml of tetrahydrofuran containing 38 g of trichloro-s-triazine, stir at 10 ° C for 16 h, ultrasonicate at 10 ° C for 4 h, and then react at 5 ° C After 72 hours, add 300ml of tetrahydrofuran, sonicate for 0.5h, then filter through a 0.8μm polytetrafluoroethylene microporous membrane, and rinse the filter cake with 500ml of tetrahydrofuran; transfer the filter cake into a 2L beaker, add 700ml of tetrahydrofuran, and sonicate for 1h, Stir at room temperature for 2 hours, and then filter through a 0.8 μm polytetrafluoroethylene microporous membrane, and wash the filter cake with 500ml tetrahydrofuran, repeat this operation 25 times, and finally dry it in vacuum at 15°C for 24 hours to obtain the active chlorine-containing trifluoride on the surface. Carbon nanotube derivatives of oxazine rings.

Get the above-mentioned carbon nanotube derivatives 5g with active chlorotriazine rings, after dissolving in 100ml N, N'-dimethylformamide, add 22g cellulose diacetate (viscosity average molecular weight is 25000, In 250ml of acetone solution with a degree of esterification of 2.3), stir at 15°C for 2h, in a 100kHz, 200W ultrasonic instrument at 15°C for 6h, heat up to 50°C for 32h under nitrogen protection, and then heat up to React at a constant temperature of 85°C for 72 hours, distill off N,N'-dimethylformamide and acetone; add 300ml of acetone, ultrasonicate for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of acetone; Transfer the cake into a 2L beaker, add 800ml of acetone, after ultrasonication for 0.5h, stir at room temperature for 2h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of acetone, repeat the operation 15 times; Wrap it in qualitative filter paper, use acetone as solvent, extract it with a Soxhlet extractor for 72 hours, and dry it in vacuum at 30°C for 48 hours to obtain a cellulose diacetate-carbon nanotube derivative product. The cellulose diacetate-carbon nanotube derivative can be used in filter materials for cigarettes.

Example 2

A cellulose diacetate-carbon nanotube derivative with a mass content ratio of cellulose diacetate and carbon nanotubes of about 1.9:1, 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 15 g of pretreated carbon nanotubes and add them to 800 ml of acetone dissolved with 70 g of phosphorus tribromide, stir at 30 ° C for 8 h, and after ultrasonic reaction at 65 ° C for 60 h, centrifuge at a speed of 5000 rpm for 30 min, wash with acetone After cleaning, vacuum-dry at 35° C. for 36 hours to obtain carbon nanotubes with acid halide functional groups on the surface.

Take 8g of the above-mentioned carbon nanotubes with acid halide functional groups on the surface, add them to 400ml of N-methylpyrrolidone containing 35g of 1,3-propylenediamine and 15ml of triethylamine, stir at 45°C for 6h, and ultrasonicate at 75°C After reacting for 32 hours, distill off N-methylpyrrolidone and triethylamine, add 200ml of mixed solvent D, ultrasonicate for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D; transfer the filter cake to Put it into a 2L beaker, add 600ml of mixed solvent D, after ultrasonication for 1h, stir at room temperature for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D, repeat the operation 15 times, and finally Vacuum drying at 20° C. for 56 hours to obtain derivatives with amino groups extending from the surface of carbon nanotubes—carbon nanotube derivatives with amino groups on the surface.

Then take 5g of the above-mentioned carbon nanotube derivatives with amino groups on the surface, add them into 400ml tetrahydrofuran containing 30g of trichloro-s-triazine, stir at 5°C for 24h, ultrasonicate at 5°C for 1h, and then react at 0°C 56h, add 200ml of acetone, sonicate for 1h, 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 500ml of acetone, and sonicate for 0.5h, Stir at room temperature for 1 hour, then suction 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.

Get the above-mentioned 1g of carbon nanotube derivatives with active chlorotriazine rings, after dissolving in 50ml N-methylpyrrolidone, add 8g of cellulose diacetate (viscosity-average molecular weight is 10000, esterification degree is 2.1 ) in 120ml of acetone solution, stirred at 20°C for 1h, ultrasonicated at 20°C for 3h in a 100kHz, 200W ultrasonic instrument, heated to 40°C for 48h under the protection of nitrogen, and then heated to 100°C for 36h , evaporate N-methylpyrrolidone and acetone; add 200ml of acetone, sonicate for 0.5h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of acetone; transfer the filter cake to a 2L beaker, add acetone 500ml, after ultrasonication for 1h, stir at room temperature for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml acetone, repeat this operation 10 times; wrap the filter cake in qualitative filter paper, use acetone as solvent , extracted with a Soxhlet extractor for 48 hours, and dried in vacuum at 30° C. for 24 hours to obtain a cellulose diacetate-carbon nanotube derivative product. The cellulose diacetate-carbon nanotube derivative can be used in filter materials for cigarettes.

Example 3

A cellulose diacetate-carbon nanotube derivative with a mass content ratio of cellulose diacetate and carbon nanotubes of about 0.6:1, the specific preparation method of which 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 1g of the pretreated carbon nanotubes and add it to 50ml of benzene and 50ml of dimethyl dissolved in 1g of thionyl chloride, stir at 30°C for 1h, and after ultrasonic reaction at 30°C for 48h, centrifuge at 3000rpm for 10min , washed with carbon tetrachloride, and vacuum-dried at 30° C. for 24 hours 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 50 ml of tetrahydrofuran and 50 ml of dimethyl sulfoxide containing 5 g of diethylene glycol and 1 ml of 3-picoline, stir at 30 ° C for 1 h, and After ultrasonic reaction at 30°C for 12 hours, evaporate tetrahydrofuran, dimethyl sulfoxide and triethylamine, add 400ml of mixed solvent D, ultrasonicate for 1 hour, then filter through a 0.8μm nylon microporous membrane, and wash the filter with 500ml of mixed solvent D Cake; transfer the filter cake into a 2L beaker, add 500ml of mixed solvent D, after ultrasonication for 2h, stir at room temperature for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D, repeat The operation was performed 20 times, and finally vacuum-dried at 10° C. for 24 hours to obtain derivatives with amino groups extending from the surface of carbon nanotubes—carbon nanotube derivatives 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 it to 50 ml of tetrahydrofuran containing 1 g of trichloro-s-triazine, stir at 0 ° C for 12 h, ultrasonicate at 0 ° C for 8 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 500ml of acetone, and sonicate for 0.5h Afterwards, stir at room temperature for 1 h, then filter through a 0.8 μm polytetrafluoroethylene microporous membrane, and rinse the filter cake with 500 ml of acetone. Carbon nanotube derivatives of chlorotriazine rings.

Take 0.1 g of the above-mentioned carbon nanotube derivatives with active chlorotriazine-containing rings, dissolve them in 50 ml of dimethyl sulfoxide, and add 1 g of cellulose diacetate (viscosity-average molecular weight is 1000, and the degree of esterification is 2.0 ) in 50ml of acetone solution, stirred at 15°C for 3h, ultrasonicated at 15°C in a 100kHz, 200W ultrasonic instrument for 1h, heated to 35°C for 12h under the protection of nitrogen, and then heated to 90°C for 24h , evaporate dimethyl sulfoxide and acetone; add 200ml of acetone, sonicate for 0.5h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of acetone; transfer the filter cake to a 2L beaker, add 500ml of acetone , after ultrasonication for 2 hours, stirred at room temperature for 1.5 hours, then filtered through a 0.8 μm nylon microporous membrane, and rinsed the filter cake with 500ml acetone, and repeated the operation 12 times; wrapped the filter cake in qualitative filter paper, and used acetone as the solvent , extracted with a Soxhlet extractor for 60 hours, and dried in vacuum at 30° C. for 36 hours to obtain a cellulose diacetate-carbon nanotube derivative product. The cellulose diacetate-carbon nanotube derivative can be used in filter materials for cigarettes.

Example 4

A cellulose diacetate-carbon nanotube derivative with a mass content ratio of cellulose diacetate and carbon nanotubes of about 8:1, 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 30g of pretreated carbon nanotubes and add them into 2000ml of N, N'-dimethylacetamide dissolved with 200g of phosphorus pentachloride, stir at 50°C for 12h, and ultrasonically react at 80°C for 72h. Centrifuge at 5000 rpm for 60 min, wash with tetrachlorofuran, and vacuum dry at 40° C. for 56 h 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 carbon tetrachloride containing 150g 1,4-butanediol and 50ml lutidine, stir at 60°C for 12h, and ultrasonicate at 90°C After reacting for 24 hours, evaporate lutidine and carbon tetrachloride, add mixed solvent D 500ml, ultrasonically 1h, then pass through 0.8μm nylon microporous filter membrane suction filtration, and rinse the filter cake with 500ml mixed solvent D; filter cake Transfer to a 2L beaker, add 1500ml of mixed solvent D, after ultrasonication for 1h, stir at room temperature for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of mixed solvent D, repeat the operation 15 times, and finally Vacuum drying at 30° C. for 72 hours to obtain derivatives with amino groups extending from the surface of carbon nanotubes—carbon nanotube derivatives with amino groups on the surface.

Then take 18g of the above-mentioned carbon nanotube derivatives with amino groups on the surface, add them to 1200ml of tetrahydrofuran containing 120g of trichloro-s-triazine, stir at 5°C for 24h, ultrasonicate at 5°C for 12h, and then react at 10°C 48h, add 500ml of acetone, sonicate for 1h, then filter through a 0.8μm polytetrafluoroethylene microporous membrane, and rinse the filter cake with 500ml of acetone; Stir for 1 hour, then filter through a 0.8 μm polytetrafluoroethylene microporous membrane, rinse the filter cake with 500 ml of acetone, repeat this operation 12 times, and finally dry it in vacuum at 10°C for 36 hours to obtain active chlorotriazine on the surface ring carbon nanotube derivatives.

Get the above-mentioned 15g of carbon nanotube derivatives with active chlorotriazine rings, after dissolving in 400ml N, N'-dimethylacetamide, add 30g of cellulose diacetate (viscosity average molecular weight is 50000, In 250ml of acetone solution with a degree of esterification of 3.0), stir at 25°C for 5h, ultrasonicate at 25°C for 12h in a 100kHz, 200W ultrasonic instrument, heat up to 40°C under nitrogen protection, and react at a constant temperature for 48h, then heat up to React at a constant temperature of 100°C for 48 hours, distill off N,N'-dimethylacetamide and acetone; add 500ml of acetone, sonicate for 0.5h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of acetone; Transfer the filter cake into a 2L beaker, add 1500ml of acetone, ultrasonic for 1h, stir at room temperature for 1h, then filter through a 0.8μm nylon microporous membrane, and rinse the filter cake with 500ml of acetone, repeat the operation 20 times; Baozi qualitative filter paper was extracted with acetone for 56 hours with a Soxhlet extractor, and vacuum-dried at 30°C for 72 hours to obtain cellulose diacetate-carbon nanotube derivatives. The cellulose diacetate-carbon nanotube derivative can be used in filter materials for cigarettes.

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

Claims (3)

1. the preparation method of a diacetyl cellulose-carbon nano-tube derivatives, it may further comprise the steps:

(1) pre-treatment of carbon nanotube;

(2) pretreated carbon nanotube and halide reagent are stirred in organic solvent A, ultrasonic then, centrifugal, after organic solvent B was cleaned, vacuum-drying at room temperature obtained the carbon nanotube that the surface has carboxylic acid halides functional group;

(3) carbon nanotube, binary functional group organic compound and the de-acidying agent that the surface is had carboxylic acid halides functional group mixes in organic solvent C, stir, ultrasonic reaction is abundant under nitrogen protection then, steaming desolventizes, again after mixed solvent D cleans, vacuum-drying at room temperature obtains the carbon nano tube derivative that surface that active functional group extends out from the surface of carbon nanotube has active functional group;

(4) carbon nano tube derivative and the trichloro-triazine that the surface is had active functional group mixes in tetrahydrofuran (THF), stir, after ultrasonic under 0-10 ℃ the low temperature, sufficient reacting under 0-10 ℃ low temperature again, after organic solvent E cleans, vacuum-drying at room temperature obtains the carbon nano tube derivative that the surface has active chloride triazine ring;

(5) after the carbon nano tube derivative that the surface is had an active chloride triazine ring dissolves in organic solvent F, join in the acetone soln that is dissolved with Cellulose diacetate, stir 1-5h down at 15-25 ℃, in the ultrasonic apparatus of 100kHz, 200W, descend ultrasonic 1-12h in 15-25 ℃, after under nitrogen protection, being warming up to 35-50 ℃ of isothermal reaction 12-48h, be warming up to 85-100 ℃ of isothermal reaction 24-72h again, steaming desolventizes; Add acetone 200-500ml, ultrasonic 0.5-1h, again by 0.8 μ m nylon millipore filtration suction filtration, and with 500ml acetone rinse filter cake; Filter cake is changed in the 2L beaker, add acetone 500-1500ml, behind the ultrasonic 0.5-2h, stirring at room 1-2h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml acetone rinse filter cake, repetitive operation like this 10-20 time; Filter cake is wrapped in the qualitative filter paper, is solvent with acetone, with cable type extractor according extracting 48-72h, obtains product behind 30 ℃ of following vacuum-drying 24-72h;

Halide reagent in the described step (2) is a kind of in phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide or the sulfur oxychloride; Organic solvent A is acetone, tetrahydrofuran (THF), benzene,toluene,xylene, methyl-sulphoxide, N-Methyl pyrrolidone, N, N '-dimethyl formamide or N, one or more in N '-N,N-DIMETHYLACETAMIDE; Organic solvent B is a kind of in acetone, ether, tetracol phenixin or the tetrahydrofuran (THF);

Binary functional group active organic compounds in the described step (3) is an ethylene glycol, 1, ammediol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, glycol ether, quadrol, 1,3-propylene diamine and 1, a kind of in the 6-hexanediamine; De-acidying agent is one or both in triethylamine, pyridine, 3-picoline and the lutidine; Organic solvent C is acetone, tetrahydrofuran (THF), tetracol phenixin, benzene,toluene,xylene, methyl-sulphoxide, N-Methyl pyrrolidone, N, N '-dimethyl formamide or N, one or more in N '-N,N-DIMETHYLACETAMIDE; Mixed solvent D is made up of acetone, ethanol and distilled water, and wherein the volume ratio of acetone, ethanol and distilled water is 2: 3: 5;

Organic solvent E in the described step (4) is a kind of in acetone or the tetrahydrofuran (THF);

The viscosity-average molecular weight of the Cellulose diacetate in the described step (5) is 1000-50000, and gamma value is 2-3; Organic solvent F is methyl-sulphoxide, N-Methyl pyrrolidone, N, N '-dimethyl formamide or N, a kind of in N '-N,N-DIMETHYLACETAMIDE.

2. according to the preparation method of a kind of diacetyl cellulose-carbon nano-tube derivatives in the claim 1, it is characterized in that: the carbon nanotube in the described step (2) is 1-30g, and halide reagent is 1-200g; Organic solvent is 100-2000ml; Agitation condition is: temperature 30-50 ℃, and time 1-12h; Ultrasound condition is: descend ultrasonic 48-72h in 30-80 ℃ in the ultrasonic apparatus of 100kHz, 200W; Centrifugal condition is: with the centrifugal 10-60min of the rotating speed of 3000-5000rpm; Vacuum drying condition is: at 20-40 ℃ of following vacuum-drying 24-56h;

Carbon nanotube in the described step (3) is 0.1-20g; Binary functional group organic compound is 5-150g; De-acidying agent is 1-50ml; Organic solvent is 100-1500ml; Agitation condition is to stir 1-12h down at 30-60 ℃; Ultrasound condition is in 30-90 ℃ of following ultrasonic 12-48h in the ultrasonic apparatus of 100kHz, 200W; The condition that mixed solvent D cleans is: add mixed solvent D 200-500ml, and ultrasonic 0.5-1h, again by 0.8 μ m nylon millipore filtration suction filtration, and with 500ml mixed solvent D rinse filter cake; Filter cake is changed in the 2L beaker, add mixed solvent D 500-1500ml, behind the ultrasonic 0.5-2h, stirring at room 1-2h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml mixed solvent D rinse filter cake, repetitive operation like this 10-20 time; Vacuum drying condition is at 10-30 ℃ of following vacuum-drying 24-72h;

Carbon nanotube in the described step (4) is 0.1-18g; Trichloro-triazine is 1-120g; Tetrahydrofuran (THF) is 50-1200ml; Agitation condition is to stir 12-24h down at 0-10 ℃; Ultrasound condition is in 0-10 ℃ of following ultrasonic 1-12h in the ultrasonic apparatus of 100kHz, 200W; Reaction conditions is to react 24-72h down at 0-10 ℃; The condition that organic solvent E cleans is: add organic solvent E200-500ml, and ultrasonic 0.5-1h, again by 0.8 μ m tetrafluoroethylene millipore filtration suction filtration, and with 500ml organic solvent E rinse filter cake; Filter cake is changed in the 2L beaker, add organic solvent E 500-1000ml, behind the ultrasonic 0.5-2h, stirring at room 1-2h, the tetrafluoroethylene millipore filtration suction filtration by 0.8 μ m again, and with 500ml organic solvent E rinse filter cake, repetitive operation like this 10-25 time; Vacuum drying condition is at 10-15 ℃ of following vacuum-drying 24-48h;

Carbon nanotube in the described step (5) is 0.1-15g; The organic solvent F of dissolved carbon nanotube is 50-400ml; Cellulose diacetate is 1-30g; Acetone is 50-250ml.

3. according to the preparation method of a kind of diacetyl cellulose-carbon nano-tube derivatives in the claim 1, it is characterized in that: the pre-treatment step of described step (1) carbon nanotube comprises: 15 diameters of respectively packing in two identical 200ml nylon jars are the Stainless Steel Ball of 6-8mm and not purified carbon nanotube 25g, drip the 10ml dehydrated alcohol more respectively, and seal with the nylon lid; Two ball grinders are put into planetary ball mill symmetrically, are 350rpm at rotating speed, and ball milling 56h under the condition of per 30 minutes automatic conversion sense of rotation, behind the hydrofluoric acid aqueous solution immersion backflow 24h with 30-50wt%, filter then, use the flowing water cleaning, drying; HNO at 2M ₃Ultrasonic 24h in the solution, backflow 24h filters, and cleans with flowing water; Be 8-10 at pH then, concentration is ultrasonic 5h in the aqueous solution of OP-10 of 20-40wt%, filters, and cleans with flowing water, after 2-3 time, immerse in the HCl solution of 3M repeatedly, and ultrasonic 12-24h, the flowing water cleaning, drying are used in filtration; Be 0.5 in volume ratio at last: 1-9.5: in 1 the vitriol oil and the concentrated nitric acid behind the ultrasonic 72-96h, backflow 72-96h, centrifugal, use the flowing water cleaning, drying, above treating processes makes its surface produce carboxyl functional group in purifying carbon nano-tube.