CN101239714B - Ethoxyl cellulose-carbon nano-tube derivatives and preparation method thereof - Google Patents
Ethoxyl cellulose-carbon nano-tube derivatives and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a droxyethylcellulose-carbon nanotube derivative, prepared by original carbon nanotube reacting with an halogenating agent after being ball grinded, purified on the base of acidizing, carboxylic acid group of the carbon nanotube surface reacting with a binary functional group organic compound to make the lively functional group extend from the surface of the carbon nanotube after being converted to acyl halide group having strong reactive activity, then reacting with trichloro triazine, obtaining a lively carbon nanotube containing trichloro triazine on the surface which can react with hydroxide radical, finally reacting with the droxyethylcellulose via nucleophilic substitution. The mass content ratio of droxyethylcellulose and carbon nanotube is 0.2-1.6:1. The invention also relates to a preparing method of the derivative. The derivative has a friendly environment, has better solubility in organic solvent such as N-pyrrolidoneextraction, dimethylsulfoxide, N, N'-dimethylformamide and N, N'-dimethyl acetamide. The preparing condition of the derivative is easy to meet, and has an ample source of feed, lower cost.
Description
Technical field
The present invention relates to a kind of derivative, particularly relate to a kind of ethoxyl cellulose-carbon nano-tube derivatives, and the preparation method of this kind derivative, belong to the natural polymer field, also belong to field of nanometer material technology.
Background technology
1991, Japanese scientist Iijima S. found carbon nanotube (Iijima S.Discovery of carbon nano-tubes.Kagaku to Kogyo, 1993,67 (12): 500-506).Through ten years development, carbon nanotube has become the important research forward position of nanosecond science and technology, and its great achievement in research emerges in an endless stream, and occupies critical role in the 21 century development in science and technology.The accurate one dimension hollow tubular structure that carbon nanotube is peculiar makes it have excellent performance aspect many in absorption, electricity, magnetics, field emission, mechanics, electrochemistry etc.Yet the solvability of extreme difference has seriously limited the research and the application of carbon nanotube.Can not only effectively improve the solvability of carbon nanotube by chemically modified, and can give its greater functionality, further widen its Application Areas.
In recent years, utilize polymer that carbon nanotube is carried out the covalent chemical modification and especially obtained extensive attention, it has become the powerful measure that preparation has the carbon nanotube and the matrix material thereof of some specific function, to researching and developing relevant nano-device and type material very big theory and realistic meaning is arranged.At present, utilize a lot of researchs of polymer covalent modification carbon nanotube mainly to concentrate on synthetic macromolecule both at home and abroad, also do not utilize the natural polymer derivative---the research report of Natvosol covalent modification carbon nanotube.Yet synthetic macromolecule is mainly derived from exhausted day by day fossil resource, and some polymers that are used for modifying also contain aromatic hydrocarbon (Feng, W. such as toxic phenyl ring; Bai, X.D.; Lian, Y.Q.; Et al.Carbon 2003,41,1551).
The ether of cellulose that obtains through etherification reaction is the plain derivative of a most important fibrid, is described as " industrial monosodium glutamate ".Natvosol is a kind of important non-ionic celluloses ether, also is the water-soluble cellulose ether that turnout is only second to carboxymethyl cellulose.Natvosol be in the cellulosic Glucopyranose ring hydroxylic moiety or all with the derivative of oxyethane open loop addition (noble and unsullied, Tang Liegui. the Mierocrystalline cellulose science. Beijing: Science Press, 1996).Different with cellulose ether derivative such as methylcellulose gum, the hydroxyl quantity in the cellulosic molecule does not reduce in hydroxyethylated process.Natvosol not only has the consistency with water-soluble polymers, tensio-active agent and salt, and the characteristic of gel-free point and set point, also has good character such as thickening, suspension and dispersion simultaneously, therefore it is (noble and unsullied to be widely used in fields such as coating, fiber, dyeing, papermaking, medicine, makeup, tackiness agent, petroleum industry, Tang Liegui. the Mierocrystalline cellulose science. Beijing: Science Press, 1996; Xu Dongsheng. derivatived cellulose. Beijing: Chemical Industry Press, 2001).
Compare with synthetic macromolecule, Natvosol is nontoxic, physiologically acceptable, biodegradable, environmental friendliness, nexhaustible renewable resources, is widely used in various fields.Because carbon nanotube and Natvosol all are the materials that has many excellent properties, therefore Natvosol is combined by covalent linkage with carbon nanotube, prepare novel ethoxyl cellulose-carbon nano-tube derivatives, be expected improving the deliquescent while of carbon nanotube, have concurrently or even be better than both performances for further developing, application prospect is arranged in fields such as high-performance separatory membrane, catalysis, environmental protection, and the novel nano matrix material of environmental protection provides a kind of base mateiral.
Summary of the invention
First purpose of the present invention provides a kind of by natural macromolecular material---the ethoxyl cellulose-carbon nano-tube derivatives of Natvosol and made of carbon nanotubes.
Second purpose of the present invention provides the preparation method of above-mentioned ethoxyl cellulose-carbon nano-tube derivatives.
First purpose of the present invention is achieved by the following technical programs:
A kind of ethoxyl cellulose-carbon nano-tube derivatives, it is that original carbon nanotube is on the basis of ball milling, purifying, acidification, react with halide reagent, after the hydroxy-acid group of carbon nano tube surface is converted into the stronger acyl halide group of reactive behavior, with binary functional group organic compound reaction, active functional group is extended out from the surface of carbon nanotube, react with trichloro-triazine again, obtain surperficial existence can with the carbon nanotube of the active chloride triazine ring of hydroxyl reaction, last and Natvosol prepares by nucleophilic substitution reaction.In this ethoxyl cellulose-carbon nano-tube derivatives, the mass content of Natvosol and carbon nanotube ratio is about 0.2-1.6: 1.
Second purpose of the present invention is achieved by the following technical programs:
A kind of preparation method of ethoxyl cellulose-carbon nano-tube derivatives, it may further comprise the steps:
1, 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;
2, above-mentioned carbon nanotube, binary functional group organic compound and the de-acidying agent that has carboxylic acid halides functional group mixed in organic solvent C, stir, ultrasonic reaction is abundant under nitrogen protection then, steaming desolventizes C and de-acidying agent, again after mixed solvent D cleans, vacuum-drying at room temperature obtains the derivative that active functional group extends out from the surface of carbon nanotube;
3, above-mentioned carbon nanotube and the trichloro-triazine that has active functional group mixed in tetrahydrofuran (THF), stir, after ultrasonic at low temperatures, sufficient reacting at low temperatures again, after organic solvent E cleans, vacuum-drying at room temperature obtains the carbon nano tube derivative that there is active chloride triazine ring in the surface;
4, the above-mentioned carbon nano tube derivative that has active chloride triazine ring is dissolved in organic solvent F after, join in the pyridine solution that is dissolved with Natvosol, 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; Adding distil water 200-500ml, ultrasonic 0.5-1h, again by 0.8 μ m nylon millipore filtration suction filtration, and with 500ml distilled water rinse filter cake; Filter cake is changed in the 2L beaker, add distilled water 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 distilled water rinse filter cake, repetitive operation like this 15-30 time; Filter cake is wrapped in the qualitative filter paper, is solvent with distilled water, with cable type extractor according extracting 48-72h, obtains product behind 30 ℃ of following vacuum-drying 24-72h.
Carbon nanotube in the above-mentioned steps 1 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.
Halide reagent in the above-mentioned steps 1 is a kind of in phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide or the sulfur oxychloride.
Organic solvent A in the above-mentioned steps 1 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 in the above-mentioned steps 1 is a kind of in acetone, ether, tetracol phenixin or the tetrahydrofuran (THF).
Carbon nanotube in the above-mentioned steps 2 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.
Binary functional group active organic compounds in the above-mentioned steps 2 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 in the above-mentioned steps 2 is one or both in triethylamine, pyridine, 3-picoline and the lutidine.
Organic solvent C in the above-mentioned steps 2 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 in the above-mentioned steps 2 is made up of acetone, ethanol and distilled water, and wherein the volume ratio of acetone, ethanol and distilled water is 2: 3: 5.
Carbon nanotube in the above-mentioned steps 3 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.
Organic solvent E in the above-mentioned steps 3 is a kind of in acetone or the tetrahydrofuran (THF).
Carbon nanotube in the above-mentioned steps 4 is 0.1-15g; The organic solvent of dissolved carbon nanotube (F) is 50-400ml; Natvosol is 1-30g; Pyridine is 50-500ml.
The viscosity-average molecular weight of the Natvosol in the above-mentioned steps 4 is 1000-30000, and substitution value is 0.1-2.5.
Organic solvent in the above-mentioned steps 4 (F) is methyl-sulphoxide, N-Methyl pyrrolidone, N, N '-dimethyl formamide or N, a kind of in N '-N,N-DIMETHYLACETAMIDE.
In the pre-treatment step of setting up before the above-mentioned steps 1 carbon nanotube: 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 in the planetary ball mill (QM-BP type, Nanjing University makes) 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.
Compared with the prior art, technical scheme of the present invention has following beneficial effect:
Ethoxyl cellulose-carbon nano-tube derivatives environmental friendliness provided by the present invention, at N-Methyl pyrrolidone, methyl-sulphoxide, N, N '-dimethyl formamide and N have good solubility in N '-organic solvents such as N,N-DIMETHYLACETAMIDE.The preparation condition of this derivative satisfies easily, and raw material sources are abundant, and cost is lower.
It is the method for feedstock production ethoxyl cellulose-carbon nano-tube derivatives that the present invention has set up with carbon nanotube and natural polymer Natvosol.Test result shows, this derivatives chemical Stability Analysis of Structures, it not only has solvability, dispersiveness and stable preferably in multiple organic solvent, the multiple excellent properties that possesses carbon nanotube and Natvosol simultaneously, be a kind of environment-friendly material, can expect its value in fields such as separate analytical technique, catalytic material, environment-friendly materials.The present invention is high in technological content, the tool novelty, and have application promise in clinical practice.
Embodiment
The present invention is first with carbon nanotube and Natvosol a kind of new derivatives that has been feedstock production.Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Embodiment 1
The mass content ratio of a kind of Natvosol and carbon nanotube is about 1.6: 1 ethoxyl cellulose-carbon nano-tube derivatives, it is that original carbon nanotube is through ball milling, purifying, on the basis of acidification, react with halide reagent, after the hydroxy-acid group of carbon nano tube surface is converted into the stronger acyl halide group of reactive behavior, with binary functional group organic compound reaction, active functional group is extended out from the surface of carbon nanotube, react with trichloro-triazine again, obtain surperficial existence can with the carbon nanotube of the active chloride triazine ring of hydroxyl reaction, last and Natvosol prepares by nucleophilic substitution reaction.Concrete preparation method is as follows:
Earlier carbon nanotube is carried out pre-treatment according to the following steps: 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 in the planetary ball mill (QM-BP type, Nanjing University makes) 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.
Getting pretreated carbon nanotube 29g then joins in the 1900ml N-Methyl pyrrolidone that is dissolved with the 190g phosphorus trichloride, stir 12h down at 50 ℃, behind 75 ℃ of following ultrasonic reaction 72h, with the centrifugal 45min of the rotating speed of 4800rpm, after cleaning with ether, at 20 ℃ of following vacuum-drying 56h, obtain the carbon nanotube that the surface has carboxylic acid halides functional group.
Get the carbon nanotube 19g that above-mentioned surface has carboxylic acid halides functional group, join and contain 140g 1, the 1400ml N of ammediol and 45ml pyridine is in N '-N,N-DIMETHYLACETAMIDE, stir 12h down at 55 ℃, behind 85 ℃ of following ultrasonic reaction 48h, steam and remove N, N '-N,N-DIMETHYLACETAMIDE and pyridine, add volume ratio and be 2: 3: 5 acetone, ethanol and distilled water mixed solvent D 450ml, ultrasonic 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 1400ml, behind the ultrasonic 1.5h, stirring at room 1h, pass through the nylon millipore filtration suction filtration of 0.8 μ m again, and mix molten D rinse filter cake with 500ml, so repetitive operation is 18 times, at last at 30 ℃ of following vacuum-drying 72h, obtain that hydroxyl extends out from the surface of carbon nanotube derivative---the surface has the carbon nano tube derivative of hydroxyl.
Get the carbon nano tube derivative 18g that above-mentioned surface has hydroxyl then, join in the 1200ml tetrahydrofuran (THF) that contains the 119g trichloro-triazine, after stirring 24h under 5 ℃, ultrasonic 11h under 10 ℃, reaction 68h under 5 ℃ adds acetone 500ml, ultrasonic 1h again, again by 0.8 μ m tetrafluoroethylene millipore filtration suction filtration, and with 500ml acetone rinse filter cake; Filter cake is changed in the 2L beaker, add acetone 1000ml, behind the ultrasonic 2h, stirring at room 2h, tetrafluoroethylene millipore filtration suction filtration by 0.8 μ m again, and with 500ml acetone rinse filter cake, repetitive operation like this 25 times, at 10 ℃ of following vacuum-drying 36h, obtain the carbon nano tube derivative that there is active chloride triazine ring in the surface at last.
Get the above-mentioned carbon nano tube derivative 15g that has active chloride triazine ring, at 400ml N, after dissolving in N '-dimethyl formamide, join and be dissolved with the 30g Natvosol (viscosity-average molecular weight is 30000, gamma value is 2.5) the 500ml pyridine solution in, stir 5h down at 15 ℃, in the ultrasonic apparatus of 100kHz, 200W, descend ultrasonic 12h in 15 ℃, after under nitrogen protection, being warming up to 50 ℃ of isothermal reaction 48h, be warming up to 100 ℃ of isothermal reaction 72h again, steam and remove N, N '-dimethyl formamide and pyridine; Adding distil water 500ml, ultrasonic 1h, again by 0.8 μ m nylon millipore filtration suction filtration, and with 500ml distilled water rinse filter cake; Filter cake is changed in the 2L beaker, add distilled water 1500ml, behind the ultrasonic 2h, stirring at room 2h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml distilled water rinse filter cake, repetitive operation like this 30 times; Filter cake is wrapped in the qualitative filter paper, is solvent with distilled water, with cable type extractor according extracting 72h, obtains the ethoxyl cellulose-carbon nano-tube derivatives product behind 30 ℃ of following vacuum-drying 72h.
Embodiment 2
The mass content ratio of a kind of Natvosol and carbon nanotube is about 0.4: 1 ethoxyl cellulose-carbon nano-tube derivatives, and its concrete preparation method is as follows:
Earlier carbon nanotube is carried out pre-treatment, this pretreatment process is identical with the foregoing description 1.
Getting pretreated carbon nanotube 15g then joins in the 900ml acetone that is dissolved with the 90g phosphorus tribromide, stir 7h down at 40 ℃, behind 65 ℃ of following ultrasonic reaction 65h, with the centrifugal 45min of the rotating speed of 4000rpm, after cleaning with ether, at 40 ℃ of following vacuum-drying 24h, obtain the carbon nanotube that the surface has carboxylic acid halides functional group.
Get the carbon nanotube 9g that above-mentioned surface has carboxylic acid halides functional group, join and contain 65g 1, in the 650ml N-Methyl pyrrolidone of 3-propylene diamine and 19ml triethylamine, stir 5h down at 30 ℃, behind 75 ℃ of following ultrasonic reaction 32h, steam and remove N-Methyl pyrrolidone and triethylamine, the adding volume ratio is 2: 3: 5 acetone, ethanol and distilled water mixed solvent D 200ml, ultrasonic 0.5h, 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 650ml, behind the ultrasonic 1h, stirring at room 1h, nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml mixed solvent D rinse filter cake, repetitive operation like this 15 times, at last at 20 ℃ of following vacuum-drying 48h, obtain that the amino derivative that extends out from the surface of carbon nanotube---the surface has amino carbon nano tube derivative.
Get above-mentioned surface then and have amino carbon nano tube derivative 9g, join in the 600ml tetrahydrofuran (THF) that contains the 60g trichloro-triazine, after stirring 12h under 10 ℃, ultrasonic 6h under 5 ℃, reaction 32h under 0 ℃ adds tetrahydrofuran (THF) 250ml, ultrasonic 0.5h again, again by 0.8 μ m tetrafluoroethylene millipore filtration suction filtration, and with 500ml tetrahydrofuran (THF) rinse filter cake; Filter cake is changed in the 2L beaker, add tetrahydrofuran (THF) 750ml, behind the ultrasonic 1h, stirring at room 1h, tetrafluoroethylene millipore filtration suction filtration by 0.8 μ m again, and with 500ml tetrahydrofuran (THF) rinse filter cake, repetitive operation like this 17 times, at 10 ℃ of following vacuum-drying 32h, obtain the carbon nano tube derivative that there is active chloride triazine ring in the surface at last.
Get the above-mentioned carbon nano tube derivative 8g that has active chloride triazine ring, after in the 300ml N-Methyl pyrrolidone, dissolving, join and be dissolved with the 15g Natvosol (viscosity-average molecular weight is 10000, gamma value is 1.2) the 300ml pyridine solution in, stir down 3h at 25 ℃, in the ultrasonic apparatus of 100kHz, 200W in 25 ℃ of ultrasonic 6h down, under nitrogen protection, be warming up to 35 ℃ of isothermal reaction 24h after, be warming up to 85 ℃ of isothermal reaction 56h again, steam and remove N-Methyl pyrrolidone and pyridine; Adding distil water 350ml, ultrasonic 0.5h, again by 0.8 μ m nylon millipore filtration suction filtration, and with 500ml distilled water rinse filter cake; Filter cake is changed in the 2L beaker, add distilled water 1000ml, behind the ultrasonic 1h, stirring at room 1h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml distilled water rinse filter cake, repetitive operation like this 24 times; Filter cake is wrapped in the qualitative filter paper, is solvent with distilled water, with cable type extractor according extracting 60h, obtains the ethoxyl cellulose-carbon nano-tube derivatives product behind 30 ℃ of following vacuum-drying 56h.
Embodiment 3
The mass content ratio of a kind of Natvosol and carbon nanotube is about 0.2: 1 ethoxyl cellulose-carbon nano-tube derivatives, and its concrete preparation method is as follows:
Earlier carbon nanotube is carried out pre-treatment, this pretreatment process is identical with the foregoing description 1.
Getting pretreated carbon nanotube 1g then joins in the 100ml dimethylbenzene that is dissolved with the 1g sulfur oxychloride, stir 1h down at 30 ℃, behind 30 ℃ of following ultrasonic reaction 48h, with the centrifugal 10min of the rotating speed of 3000rpm, after cleaning with tetracol phenixin, at 30 ℃ of following vacuum-drying 48h, obtain the carbon nanotube that the surface has carboxylic acid halides functional group.
Get the carbon nanotube 0.1g that above-mentioned surface has carboxylic acid halides functional group, join in the 100ml tetrahydrofuran (THF) that contains 5g glycol ether and 1ml lutidine, stir 1h down at 60 ℃, under nitrogen protection, behind 30 ℃ of ultrasonic reaction 12h, steam and remove tetrahydrofuran (THF) and lutidine, add volume ratio and be 2: 3: 5 acetone, ethanol and distilled water mixed solvent D 300ml, ultrasonic 0.5h, 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 500ml, behind the ultrasonic 0.5h, stirring at room 2h, 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 times, at last at 10 ℃ of following vacuum-drying 24h, obtain that the amino derivative that extends out from the surface of carbon nanotube---the surface has amino carbon nano tube derivative.
Get above-mentioned surface then and have amino carbon nano tube derivative 0.1g, join in the 50ml tetrahydrofuran (THF) that contains the 1g trichloro-triazine, after stirring 18h under 0 ℃, ultrasonic 1h under 0 ℃, reaction 24h under 10 ℃ adds acetone 400ml, ultrasonic 0.5h again, again by 0.8 μ m tetrafluoroethylene millipore filtration suction filtration, and with 500ml acetone rinse filter cake; Filter cake is changed in the 2L beaker, add acetone 750ml, behind the ultrasonic 1h, stirring at room 1h, tetrafluoroethylene millipore filtration suction filtration by 0.8 μ m again, and with 500ml acetone rinse filter cake, repetitive operation like this 10 times, at 15 ℃ of following vacuum-drying 24h, obtain the carbon nano tube derivative that there is active chloride triazine ring in the surface at last.
Get the above-mentioned carbon nano tube derivative 0.1g that has active chloride triazine ring, after in the 50ml methyl-sulphoxide, dissolving, join and be dissolved with the 1g Natvosol (viscosity-average molecular weight is 1000, gamma value is 0.1) the 50ml pyridine solution in, stir down 1h at 20 ℃, in the ultrasonic apparatus of 100kHz, 200W in 20 ℃ of ultrasonic 1h down, under nitrogen protection, be warming up to 40 ℃ of isothermal reaction 12h after, be warming up to 90 ℃ of isothermal reaction 24h again, steam and remove in the methyl-sulphoxide and pyridine; Adding distil water 200ml, ultrasonic 0.5h, again by 0.8 μ m nylon millipore filtration suction filtration, and with 500ml distilled water rinse filter cake; Filter cake is changed in the 2L beaker, add distilled water 500ml, behind the ultrasonic 1h, stirring at room 1h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml distilled water rinse filter cake, repetitive operation like this 15 times; Filter cake is wrapped in the qualitative filter paper, is solvent with distilled water, with cable type extractor according extracting 48h, obtains the ethoxyl cellulose-carbon nano-tube derivatives product behind 30 ℃ of following vacuum-drying 24h.
The present invention is not limited to above embodiment, so long as the scheme of mentioning in this specification sheets all can be implemented.
Claims (8)
1. ethoxyl cellulose-carbon nano-tube derivatives, it is that original carbon nanotube is through ball milling, purifying, on the basis of acidification, react with halide reagent, after the hydroxy-acid group of carbon nano tube surface is converted into the stronger acyl halide group of reactive behavior, with binary functional group organic compound reaction, active functional group is extended out from the surface of carbon nanotube, react with trichloro-triazine again, obtain surperficial existence can with the carbon nanotube of the active chloride triazine ring of hydroxyl reaction, last and Natvosol prepares by nucleophilic substitution reaction, in this ethoxyl cellulose-carbon nano-tube derivatives, the mass content of Natvosol and carbon nanotube is than being 0.2-1.6: 1.
2. the preparation method of an ethoxyl cellulose-carbon nano-tube derivatives, it may further comprise the steps:
(1) 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;
(2) above-mentioned carbon nanotube, binary functional group organic compound and the de-acidying agent that has carboxylic acid halides functional group mixed in organic solvent C, stir, ultrasonic reaction is abundant under nitrogen protection then, steaming desolventizes C and de-acidying agent, again after mixed solvent D cleans, vacuum-drying at room temperature obtains the derivative that active functional group extends out from the surface of carbon nanotube;
(3) above-mentioned carbon nanotube and the trichloro-triazine that has active functional group mixed in tetrahydrofuran (THF), stir, after ultrasonic at low temperatures, again at 0-10 ℃ of following sufficient reacting, after organic solvent E cleans, vacuum-drying at room temperature obtains the carbon nano tube derivative that there is active chloride triazine ring in the surface;
(4) the above-mentioned carbon nano tube derivative that has active chloride triazine ring is dissolved in organic solvent F after, join in the pyridine solution that is dissolved with Natvosol, 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; Adding distil water 200-500ml, ultrasonic 0.5-1h, again by 0.8 μ m nylon millipore filtration suction filtration, and with 500ml distilled water rinse filter cake; Filter cake is changed in the 2L beaker, add distilled water 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 distilled water rinse filter cake, repetitive operation like this 15-30 time; Filter cake is wrapped in the qualitative filter paper, is solvent with distilled water, with cable type extractor according extracting 48-72h, obtains product behind 30 ℃ of following vacuum-drying 24-72h.
3. the preparation method of a kind of ethoxyl cellulose-carbon nano-tube derivatives according to claim 2, it is characterized in that: the carbon nanotube in the described step (1) is 1-30g, halide reagent is 1-200g; Organic solvent A 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.
4. the preparation method of a kind of ethoxyl cellulose-carbon nano-tube derivatives according to claim 2, it is characterized in that: the carbon nanotube in the described step (2) 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 D200-500ml, 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.
5. the preparation method of a kind of ethoxyl cellulose-carbon nano-tube derivatives according to claim 2, it is characterized in that: the carbon nanotube in the described step (3) 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 E 200-500ml, 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.
6. the preparation method of a kind of ethoxyl cellulose-carbon nano-tube derivatives according to claim 2, it is characterized in that: the carbon nanotube in the described step (4) is 0.1-15g; The organic solvent F of dissolved carbon nanotube is 50-400ml; Natvosol is 1-30g; Pyridine is 50-500ml; The viscosity-average molecular weight of described Natvosol is 1000-30000, and substitution value is 0.1-2.5.
7. the preparation method of a kind of ethoxyl cellulose-carbon nano-tube derivatives according to claim 2 is characterized in that: the halide reagent in the described step (1) is a kind of in phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide or the sulfur oxychloride; Described 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; Described 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 (2) 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; Described de-acidying agent is one or both in triethylamine, pyridine, 3-picoline and the lutidine; Described 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; Described 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 (3) is a kind of in acetone or the tetrahydrofuran (THF); Organic solvent F in the described step (4) is methyl-sulphoxide, N-Methyl pyrrolidone, N, N '-dimethyl formamide or N, a kind of in N '-N,N-DIMETHYLACETAMIDE.
8. the preparation method of a kind of ethoxyl cellulose-carbon nano-tube derivatives according to claim 2, it is characterized in that: set up pre-treatment step to carbon nanotube before in described step (1): 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.
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| WO2004097853A1 (en) * | 2003-04-24 | 2004-11-11 | Carbon Nanotechnologies, Inc. | Conductive carbon nanotube-polymer composite |
| CN101098921A (en) * | 2005-01-05 | 2008-01-02 | 阿克马法国公司 | Use of carbon nanotubes for the production of a conductive organic composition and applications of one such composition |
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| WO2004097853A1 (en) * | 2003-04-24 | 2004-11-11 | Carbon Nanotechnologies, Inc. | Conductive carbon nanotube-polymer composite |
| CN101098921A (en) * | 2005-01-05 | 2008-01-02 | 阿克马法国公司 | Use of carbon nanotubes for the production of a conductive organic composition and applications of one such composition |
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