CN101239715B - Diacetyl cellulose-carbon nano-tube derivatives, preparation method and use thereof - Google Patents
Diacetyl cellulose-carbon nano-tube derivatives, preparation method and use thereof Download PDFInfo
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- CN101239715B CN101239715B CN2008100266404A CN200810026640A CN101239715B CN 101239715 B CN101239715 B CN 101239715B CN 2008100266404 A CN2008100266404 A CN 2008100266404A CN 200810026640 A CN200810026640 A CN 200810026640A CN 101239715 B CN101239715 B CN 101239715B
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Abstract
he present invention provides a cellulose diacetate-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 cellulose diacetate via nucleophilic substitution. The mass content ratio of cellulose diacetate and carbon nanotube is 0.6-8:1. The invention also relates to a preparing method and purpose of the derivative. The derivative has a friendly environment, and a better solubility. The preparing condition of the derivative is easy to meet, and has an ample source of feed, lower cost, has high price in the filtering material for tobacco.
Description
Technical field
The present invention relates to a kind of derivative, particularly relate to a kind of diacetyl cellulose-carbon nano-tube derivatives, and the preparation method of this kind derivative and purposes, 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 cellulose acetate 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).
Cellulose acetate is found in 1869, is one of derivatived cellulose of studying the earliest and producing, and also is the vital cellulose organic ester of generally acknowledging; Wherein, gamma value is that the Cellulose diacetate of 2-3 dissolves in acetone, be widely used at present making cigarette filter filament, high-performance separation membrane material, textile materials, coating, plastics etc. (noble and unsullied, Tang Liegui. the Mierocrystalline cellulose science. Beijing: Science Press, 1996; Xu Dongsheng. derivatived cellulose. Beijing: Chemical Industry Press, 2001).
Compare with synthetic macromolecule, Cellulose diacetate is nontoxic, physiologically acceptable, biodegradable, environmental friendliness, nexhaustible renewable resources, is widely used in various fields.Therefore, Cellulose diacetate can be used as the desirable polymer of covalent modification carbon nanotube.Because carbon nanotube and Cellulose diacetate all are the materials that has many excellent properties, therefore Cellulose diacetate is combined by covalent linkage with carbon nanotube, be expected improving the deliquescent while of carbon nanotube, develop and have concurrently or even be better than both performances, with fields such as filter materials application prospect, the novel nano matrix material of environmental protection are arranged at cigarette.
Summary of the invention
First purpose of the present invention provides a kind of by natural macromolecular material---the diacetyl cellulose-carbon nano-tube derivatives of Cellulose diacetate and made of carbon nanotubes.
Second purpose of the present invention provides the preparation method of above-mentioned diacetyl cellulose-carbon nano-tube derivatives.
The 3rd purpose of the present invention provides the purposes of above-mentioned diacetyl cellulose-carbon nano-tube derivatives.
First purpose of the present invention is achieved by the following technical programs:
A kind of diacetyl 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 Cellulose diacetate prepares by nucleophilic substitution reaction.In this diacetyl cellulose-carbon nano-tube derivatives, the mass content of Cellulose diacetate and carbon nanotube ratio is about 0.6-8: 1.
Second purpose of the present invention is achieved by the following technical programs:
A kind of preparation method of diacetyl cellulose-carbon nano-tube derivatives, it may further comprise the steps:
1, carbon nanotube is carried out pre-treatment;
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, 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, steam and remove organic solvent 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;
4, 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;
5, the above-mentioned carbon nano tube derivative that has active chloride triazine ring is dissolved in organic solvent F after, 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, steam and remove organic solvent F and acetone; 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.
Carbon nanotube in the above-mentioned steps 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.
Halide reagent in the above-mentioned steps 2 is a kind of in phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide or the sulfur oxychloride.
Organic solvent A in the above-mentioned steps 2 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 2 is a kind of in acetone, ether, tetracol phenixin or the tetrahydrofuran (THF).
Carbon nanotube in the above-mentioned steps 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 D500-1500ml, 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 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 in the above-mentioned steps 3 is one or both in triethylamine, pyridine, 3-picoline and the lutidine.
Organic solvent C in the above-mentioned steps 3 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 3 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 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.
Organic solvent E in the above-mentioned steps 4 is a kind of in acetone or the tetrahydrofuran (THF).
Carbon nanotube in the above-mentioned steps 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.
The viscosity-average molecular weight of the Cellulose diacetate in the above-mentioned steps 5 is 1000-50000, and gamma value is 2-3.
Organic solvent F in the above-mentioned steps 5 is methyl-sulphoxide, N-Methyl pyrrolidone, N, N '-dimethyl formamide or N, a kind of in N '-N,N-DIMETHYLACETAMIDE.
The pre-treatment of described step 1 pair carbon nanotube is undertaken by 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.
The 3rd purpose of the present invention realizes by following scheme:
The application of a kind of diacetyl cellulose-carbon nano-tube derivatives of the present invention in cigarette usefulness filtering material.With the mass content ratio of Cellulose diacetate and carbon nanotube is that 1.9: 1 diacetyl cellulose-carbon nano-tube derivatives is an example, according to " People's Republic of China's industry standard (cigarette): measure total particulate matter and tar (industry standard) with smoking machine with routine analysis, 1996 ", with a kind of cigarette filter (lesser panda board, Guangzhou cigar mill) for contrasting thing, identical in quality, and under the situation of test conditions unanimity, the filter tip (mass content of this derivative is 25%) that contains this derivative can the former raising respectively 31% and 26% of force rate to the removal of Nicotine and tar.
Compared with the prior art, technical scheme of the present invention has following beneficial effect:
Diacetyl cellulose-carbon nano-tube derivatives environmental friendliness provided by the present invention, energy minimal amounts of dissolved in acetone, at methyl-sulphoxide, N-Methyl pyrrolidone, 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 diacetyl cellulose-carbon nano-tube derivatives that the present invention has set up with carbon nanotube and natural polymer Cellulose diacetate.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 Cellulose diacetate simultaneously, be a kind of environment-friendly material, can expect that it is in the value of cigarette with fields such as filtering 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 Cellulose diacetate 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 Cellulose diacetate and carbon nanotube is about 3.2: 1 diacetyl 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 Cellulose diacetate 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 20g then joins in the 1000ml N-Methyl pyrrolidone that is dissolved with the 100g phosphorus trichloride, stir 10h down at 40 ℃, behind 75 ℃ of following ultrasonic reaction 72h, with the centrifugal 60min of the rotating speed of 4000rpm, after cleaning with ether, at 20 ℃ of following vacuum-drying 48h, obtain the carbon nanotube that the surface has carboxylic acid halides functional group.
Get the carbon nanotube 15g that above-mentioned surface has carboxylic acid halides functional group, join and contain 50g 1, the 600ml N of ammediol and 25ml pyridine is in N '-N,N-DIMETHYLACETAMIDE, stir 10h down at 60 ℃, behind 85 ℃ of following ultrasonic reaction 48h, steam and remove N, N '-N,N-DIMETHYLACETAMIDE and pyridine, add 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 800ml, 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 30 ℃ of following vacuum-drying 48h, 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 10g that above-mentioned surface has hydroxyl then, join in the 700ml tetrahydrofuran (THF) that contains the 38g trichloro-triazine, after stirring 16h under 10 ℃, ultrasonic 4h under 10 ℃, reaction 72h under 5 ℃ adds tetrahydrofuran (THF) 300ml, 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) 700ml, behind the ultrasonic 1h, stirring at room 2h, tetrafluoroethylene millipore filtration suction filtration by 0.8 μ m again, and with 500ml tetrahydrofuran (THF) rinse filter cake, repetitive operation like this 25 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 5g that has active chloride triazine ring, at 100ml N, after the dissolving, join in the 250ml acetone soln that is dissolved with 22g Cellulose diacetate (viscosity-average molecular weight is 25000, and gamma value is 2.3) in N '-dimethyl formamide, stir 2h down at 15 ℃, in the ultrasonic apparatus of 100kHz, 200W in 15 ℃ of following ultrasonic 6h, under nitrogen protection, be warming up to 50 ℃ of isothermal reaction 32h after, be warming up to 85 ℃ of isothermal reaction 72h again, steam and remove N, N '-dimethyl formamide and acetone; Add acetone 300ml, ultrasonic 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 800ml, behind the ultrasonic 0.5h, stirring at room 2h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml acetone rinse filter cake, repetitive operation like this 15 times; Filter cake is wrapped in the qualitative filter paper, is solvent with acetone, with cable type extractor according extracting 72h, obtains the diacetyl cellulose-carbon nano-tube derivatives product behind 30 ℃ of following vacuum-drying 48h.This diacetyl cellulose-carbon nano-tube derivatives can be used in filtering material at cigarette.
Embodiment 2
The mass content ratio of a kind of Cellulose diacetate and carbon nanotube is about 1.9: 1 diacetyl 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 800ml acetone that is dissolved with the 70g phosphorus tribromide, stir 8h down at 30 ℃, behind 65 ℃ of following ultrasonic reaction 60h, with the centrifugal 30min of the rotating speed of 5000rpm, after cleaning with acetone, at 35 ℃ of following vacuum-drying 36h, obtain the carbon nanotube that the surface has carboxylic acid halides functional group.
Get the carbon nanotube 8g that above-mentioned surface has carboxylic acid halides functional group, join and contain 35g 1, in the 400mlN-methyl-2-pyrrolidone of 3-propylene diamine and 15ml triethylamine, stir 6h down at 45 ℃, behind 75 ℃ of following ultrasonic reaction 32h, steam and remove N-Methyl pyrrolidone and triethylamine, add mixed solvent D200ml, 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 600ml, 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 56h, 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 5g, join in the 400ml tetrahydrofuran (THF) that contains the 30g trichloro-triazine, after stirring 24h under 5 ℃, ultrasonic 1h under 5 ℃, reaction 56h under 0 ℃ adds acetone 200ml, 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 500ml, behind the ultrasonic 0.5h, 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 15 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 1g that has active chloride triazine ring, after in the 50ml N-Methyl pyrrolidone, dissolving, join and be dissolved with the 8g Cellulose diacetate (viscosity-average molecular weight is 10000, gamma value is 2.1) the 120ml acetone soln in, stir down 1h at 20 ℃, in the ultrasonic apparatus of 100kHz, 200W in 20 ℃ of ultrasonic 3h down, under nitrogen protection, be warming up to 40 ℃ of isothermal reaction 48h after, be warming up to 100 ℃ of isothermal reaction 36h again, steam and remove N-Methyl pyrrolidone and acetone; Add acetone 200ml, ultrasonic 0.5h, 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 500ml, behind the ultrasonic 1h, stirring at room 1h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml acetone rinse filter cake, repetitive operation like this 10 times; Filter cake is wrapped in the qualitative filter paper, is solvent with acetone, with cable type extractor according extracting 48h, obtains the diacetyl cellulose-carbon nano-tube derivatives product behind 30 ℃ of following vacuum-drying 24h.This diacetyl cellulose-carbon nano-tube derivatives can be used in filtering material at cigarette.
Embodiment 3
The mass content ratio of a kind of Cellulose diacetate and carbon nanotube is about 0.6: 1 diacetyl 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 50ml benzene and 50ml dimethyl that dissolves 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 24h, 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 50ml tetrahydrofuran (THF) and 50ml methyl-sulphoxide that contains 5g glycol ether and 1ml 3-picoline, stir 1h down at 30 ℃, behind 30 ℃ of following ultrasonic reaction 12h, steam and remove tetrahydrofuran (THF), methyl-sulphoxide and triethylamine, add mixed solvent D 400ml, 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 500ml, behind the ultrasonic 2h, 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 20 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 50m1 tetrahydrofuran (THF) that contains the 1g trichloro-triazine, after stirring 12h under 0 ℃, ultrasonic 8h under 0 ℃, reaction 24h under 0 ℃ adds acetone 200ml, 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 500ml, behind the ultrasonic 0.5h, 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 10 ℃ of following vacuum-drying 48h, 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 Cellulose diacetate (viscosity-average molecular weight is 1000, gamma value is 2.0) the 50ml acetone soln in, stir down 3h at 15 ℃, in the ultrasonic apparatus of 100kHz, 200W in 15 ℃ of ultrasonic 1h down, under nitrogen protection, be warming up to 35 ℃ of isothermal reaction 12h after, be warming up to 90 ℃ of isothermal reaction 24h again, steam and remove methyl-sulphoxide and acetone; Add acetone 200ml, ultrasonic 0.5h, 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 500ml, behind the ultrasonic 2h, stirring at room 1.5h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml acetone rinse filter cake, repetitive operation like this 12 times; Filter cake is wrapped in the qualitative filter paper, is solvent with acetone, with cable type extractor according extracting 60h, obtains the diacetyl cellulose-carbon nano-tube derivatives product behind 30 ℃ of following vacuum-drying 36h.This diacetyl cellulose-carbon nano-tube derivatives can be used in filtering material at cigarette.
Embodiment 4
The mass content ratio of a kind of Cellulose diacetate and carbon nanotube is about 8: 1 diacetyl 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.
Get pretreated carbon nanotube 30g then and join the 2000ml N that is dissolved with the 200g phosphorus pentachloride, in N '-N,N-DIMETHYLACETAMIDE, stir 12h down at 50 ℃, behind 80 ℃ of following ultrasonic reaction 72h, with the centrifugal 60min of the rotating speed of 5000rpm, after cleaning with the tetrachloro furans,, obtain the carbon nanotube that the surface has carboxylic acid halides functional group at 40 ℃ of following vacuum-drying 56h.
Get the carbon nanotube 20g that above-mentioned surface has carboxylic acid halides functional group, join and contain 150g 1, in the 1500ml tetracol phenixin of 4-butyleneglycol and 50ml lutidine, stir 12h down at 60 ℃, behind 90 ℃ of following ultrasonic reaction 24h, steam and remove lutidine and tetracol phenixin, add mixed solvent D 500ml, 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 1500ml, 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 30 ℃ of following vacuum-drying 72h, 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 18g, join in the 1200ml tetrahydrofuran (THF) that contains the 120g trichloro-triazine, after stirring 24h under 5 ℃, ultrasonic 12h under 5 ℃, reaction 48h under 10 ℃ 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 1500ml, behind the ultrasonic 2h, 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 12 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 '-N,N-DIMETHYLACETAMIDE, join and be dissolved with the 30g Cellulose diacetate (viscosity-average molecular weight is 50000, gamma value is 3.0) the 250ml acetone soln in, stir 5h down at 25 ℃, in the ultrasonic apparatus of 100kHz, 200W, descend ultrasonic 12h in 25 ℃, after under nitrogen protection, being warming up to 40 ℃ of isothermal reaction 48h, be warming up to 100 ℃ of isothermal reaction 48h again, steam and remove N, N '-N,N-DIMETHYLACETAMIDE and acetone; Add acetone 500ml, ultrasonic 0.5h, 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 1500ml, behind the ultrasonic 1h, stirring at room 1h, the nylon millipore filtration suction filtration by 0.8 μ m again, and with 500ml acetone rinse filter cake, repetitive operation like this 20 times; In filter cake steamed stuffed bun qualitative filter paper, be solvent with acetone, with cable type extractor according extracting 56h, behind 30 ℃ of following vacuum-drying 72h, obtain the diacetyl cellulose-carbon nano-tube derivatives product.This diacetyl cellulose-carbon nano-tube derivatives can be used in filtering material at cigarette.
The present invention is not limited to above scheme, so long as the scheme of mentioning in this specification sheets all 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.
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