CN1587031A - Process for preparing surface carboxyl modified carbon nano tube - Google Patents
Process for preparing surface carboxyl modified carbon nano tube Download PDFInfo
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Abstract
The present invention relates to the preparation process of surface carboxyl modified carbon nanotube. Carbon nanotube is first surface modified with azo initiator containing cyano group, and the cyano group is then hydrolyzed in alkaline or acid condition to obtain the surface carboxyl modified carbon nanotube. The present invention has simple process and easy-to-obtain material, and the prepared carboxylated carbon nanotube has the complete structure maintained and number controllable surface carboxyl group.
Description
Technical field
The invention belongs to technical field of inorganic material, be specifically related to a kind of preparation method of carbon nanotube of surface carboxyl modification.
Technical background
Carbon nanotube is the nano level coaxial clyinder of the seamless hollow that is rolled into of the graphite by laminated structure, cylindrical two ends respectively have one " cap " that formed by half soccerballene spheroid molecule, generally can divide for the Single Walled Carbon Nanotube be made up of one deck graphite and by two kinds of the coaxial multi-walled carbon nano-tubes of forming of multilayer graphite.
Because the distinctive immanent structure of carbon nanotube (length-to-diameter ratio, chirality etc.), carbon nanotube shows peculiar physical properties, is a kind of type material that catches people's attention.Can be used for preparing field emission device, nano electron device and one dimension gan nanometer rod.Carbon nanotube is a kind of potential hydrogen storage material, and is one of mechanical property best material since the dawn of human civilization, has very big using value aspect polymer blending.But because carbon nanotube has huge molecular weight, directly caused the insolubility of carbon nanotube, thereby limited the application of carbon nanotube in a lot of fields.Therefore, the preparation of soluble carbon nanotube becomes a difficult problem of being badly in need of solution, also becomes the popular direction of scientists study.In the preparation process of soluble carbon nanotube, the carbon nanotube of carboxyl surface modification occupies an important position, and a lot of preparation process all are through carboxy-modified process.
With regard to the surface carboxyl modification of carbon nanotube, institute's employing method of bibliographical information is mainly and uses the nitric acid treatment carbon nanotube at present.The carbon nanotube of the surface carboxyl modification that this method obtains, the carboxyl quantity on surface is uncontrollable, and obtain the surface carboxylated in, carbon nanotube can be by brachymemma, thereby has destroyed the original structure of carbon nanotube.
Because carbon nanotube is by brachymemma, application, the particularly application of polymer blending material aspect in a lot of fields have been subjected to very big restriction.In the carbon nanotube polymer intermingling material, the longer the better to require the length of carbon nanotube.
Among the present invention, we have proposed the novel method of the carboxylated modified carbon nano-tube in a kind of simple preparation surface, and raw material is easy to get, the preparation process good reproducibility, the carbon nanotube carboxyl controllable number of the surface carboxyl modification that makes, carbon nanotube keeps original structure, not by brachymemma.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of new carboxyl surface-modified carbon nanotubes.
The preparation method of carbon nano-tube of a kind of surface carboxyl modification that the present invention proposes, azo-initiator with cyano-containing carries out surface modification to carbon nanotube, in acidity or alkaline system, cyano group is hydrolyzed then, thereby obtain the carbon nanotube of surface carboxyl modification, wherein, the control surface carboxyl accounts for the 1-90% of carbon nanotube gross weight.
Among the present invention, described azo-initiator with cyano-containing is as follows to the step that carbon nanotube carries out modification: the carbon nanotube ultra-sonic dispersion in coordinative solvent, is added the azo-initiator of cyano-containing then, logical nitrogen 20-40 minute, be warming up to 60-80 ℃, reaction, 90-150 minute; Isolate the azo-initiator modified carbon nanotube of cyano-containing then with filtering with microporous membrane, and wash 3-5 time with coordinative solvent.
Among the present invention, the described step that cyano group is hydrolyzed is as follows: the azo-initiator modified carbon nanotube of the cyano-containing of gained is added in acidic aqueous solution or the alkaline aqueous solution, backflow 90-150 minute, use filtering with microporous membrane then, isolate carboxy-modified carbon nanotube, and with deionized water wash 3-5 time; At last, put into vacuum drying oven, 35-50 ℃ of drying obtains the carbon nanotube of carboxyl surface modification.
Among the present invention, used carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, and used solvent is toluene, tetrahydrofuran (THF), N, one or more in dinethylformamide, the N-Methyl pyrrolidone.
Among the present invention, the azo-initiator of used cyano-containing is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two different caprylic nitriles, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 1, one or more in 1 '-azo two (cyclohexanenitrile).
Among the present invention, used acid is one or more in hydrochloric acid, sulfuric acid, the phosphoric acid, and used alkali is one or more in sodium hydroxide, the potassium hydroxide.
Among the present invention, used millipore filtration is PVDF membrane or the poly tetrafluoroethylene of 0.30-0.60 μ m.
The preparation method of the surface carboxyl modification carbon nanotube that the present invention proposes, with the azo-initiator modified carbon nano-tube of cyano-containing, hydrolysis cyano group obtains the surface carboxyl modification carbon nanotube then with earlier.Surface carboxyl controllable number, usually, 1%~90% of the weight of hydroxyl and whole modified carbon nano-tube weight.In whole process, the not original structure of destroying carbon nanometer tube, not shortening carbon nano-tube.
The surface carboxyl modification of at present domestic and international carbon nanotube mainly adopts the method for nitric acid oxidation, and comparatively speaking, the present invention avoids adopting the strong acid of strong oxidizing property.Have following characteristics: the carboxyl controllable number (2) of (1) surface modification of carbon nanotube is the original structure of destroying carbon nanometer tube, not shortening carbon nano-tube not.
Embodiment
Embodiment 1: in the 100mL three-necked bottle, add 30mg multi-wall carbon nano-tube pipe powder, add the toluene of 50mL, the ultrasonic multi-walled carbon nano-tubes that makes is uniformly dispersed, and adds the 2g Diisopropyl azodicarboxylate then, the logical nitrogen deoxygenation of room temperature 25 minutes.Be warming up to 60 ℃ then, react stop after 120 minutes the heating, reduce to room temperature.Isolate the multi-walled carbon nano-tubes of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with toluene wash 3~5 times.
In single neck round-bottomed flask of a 100mL, the aqueous sodium hydroxide solution that adds 50mL 2mol/L, the multi-walled carbon nano-tubes that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 90 minutes is after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 3~5 times, 40 ℃ of dryings of vacuum drying oven are spent the night, and obtain the multi-walled carbon nano-tubes of carboxyl surface modification.
Embodiment 2: in the 100mL three-necked bottle, add 25mg Single Walled Carbon Nanotube powder, add the tetrahydrofuran (THF) of 50mL, the ultrasonic Single Walled Carbon Nanotube that makes is uniformly dispersed, and adds the 5g Diisopropyl azodicarboxylate then, the logical nitrogen deoxygenation of room temperature 30 minutes.Be warming up to 65 ℃ then, react stop after 90 minutes the heating, reduce to room temperature.Isolate the Single Walled Carbon Nanotube of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and wash 3~5 times with tetrahydrofuran (THF).
In single neck round-bottomed flask of a 100mL, the potassium hydroxide aqueous solution that adds 50mL 2mol/L, the Single Walled Carbon Nanotube that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 120 minutes, after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 3~5 times, 35 ℃ of dried overnight of vacuum drying oven obtain the Single Walled Carbon Nanotube of carboxyl surface modification.
Embodiment 3: in the 100mL three-necked bottle, add 30mg multi-wall carbon nano-tube pipe powder, add the toluene of 70mL, the ultrasonic multi-walled carbon nano-tubes that makes is uniformly dispersed, and adds the 2g Diisopropyl azodicarboxylate then, the logical nitrogen deoxygenation of room temperature 0.5 hour.Be warming up to 70 ℃ then, react stop after 2 hours the heating, reduce to room temperature.Isolate the multi-walled carbon nano-tubes of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with toluene wash 3~5 times.
In single neck round-bottomed flask of a 100mL, the aqueous hydrochloric acid that adds 50mL 2mol/L, the multi-walled carbon nano-tubes that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 140 minutes, after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 5 times, 35 ℃ of dried overnight of vacuum drying oven obtain the multi-walled carbon nano-tubes of carboxyl surface modification.
Embodiment 4: in the 100mL three-necked bottle, add 30mg Single Walled Carbon Nanotube powder, add the N-Methyl pyrrolidone of 50mL, the ultrasonic Single Walled Carbon Nanotube that makes is uniformly dispersed, and adds the 2g Diisopropyl azodicarboxylate then, the logical nitrogen deoxygenation of room temperature 35 minutes.Be warming up to 75 ℃ then, react stop after 120 minutes the heating, reduce to room temperature.Isolate the Single Walled Carbon Nanotube of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and wash 3~5 times with N-Methyl pyrrolidone.
In single neck round-bottomed flask of a 100mL, the aqueous hydrochloric acid that adds 50mL 2mol/L, the Single Walled Carbon Nanotube that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 90 minutes, after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 3~5 times, 40 ℃ of dried overnight of vacuum drying oven obtain the Single Walled Carbon Nanotube of carboxyl surface modification.
Embodiment 5: in the 100mL three-necked bottle, add 30mg multi-wall carbon nano-tube pipe powder, add the toluene of 50mL and N-Methyl pyrrolidone arbitrarily than mixed solvent, the ultrasonic multi-walled carbon nano-tubes that makes is uniformly dispersed, add the 20g Diisopropyl azodicarboxylate then, the logical nitrogen deoxygenation of room temperature 25 minutes is warming up to 65 ℃ then, react stop after 100 minutes the heating, reduce to room temperature.Isolate the multi-walled carbon nano-tubes of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with toluene wash 3~5 times.
In single neck round-bottomed flask of a 100mL, the aqueous sodium hydroxide solution that adds 50mL 2mol/L, the multi-walled carbon nano-tubes that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 2 hours, after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 3~5 times, 40 ℃ of dried overnight of vacuum drying oven obtain the multi-walled carbon nano-tubes of carboxyl surface modification.
Embodiment 6: in the 100mL three-necked bottle, add 30mg multi-wall carbon nano-tube pipe powder, add the toluene of 50mL, the ultrasonic multi-walled carbon nano-tubes that makes is uniformly dispersed, and adds the 20g 2,2'-Azobis(2,4-dimethylvaleronitrile) then, the logical nitrogen deoxygenation of room temperature 0.5 hour.Be warming up to 70 ℃ then, react stop after 140 minutes the heating, reduce to room temperature.Isolate the multi-walled carbon nano-tubes of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and wash 3~5 times with tetrahydrofuran (THF).
In single neck round-bottomed flask of a 100mL, the aqueous sodium hydroxide solution that adds 50mL 2mol/L, the multi-walled carbon nano-tubes that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 100 minutes, after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 3~5 times, 35 ℃ of dried overnight of vacuum drying oven obtain the multi-walled carbon nano-tubes of carboxyl surface modification.
Embodiment 7: in the 100mL three-necked bottle, add 30mg multi-wall carbon nano-tube pipe powder, add the N-Methyl pyrrolidone of 50mL, the ultrasonic multi-walled carbon nano-tubes that makes is uniformly dispersed, and adds 20g azo two different caprylic nitriles then, the logical nitrogen deoxygenation of room temperature 30 minutes.Be warming up to 65 ℃ then, react stop after 150 minutes the heating, reduce to room temperature.Isolate the multi-walled carbon nano-tubes of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and wash 3~5 times with N-Methyl pyrrolidone.
In single neck round-bottomed flask of a 100mL, the aqueous sodium hydroxide solution that adds 50mL 2mol/L, the multi-walled carbon nano-tubes that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 130 minutes, after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 3~5 times, 40 ℃ of dried overnight of vacuum drying oven obtain the multi-walled carbon nano-tubes of carboxyl surface modification.
Embodiment 8: in the 100mL three-necked bottle, add 30mg multi-wall carbon nano-tube pipe powder, add the N of 50mL, dinethylformamide, the ultrasonic multi-walled carbon nano-tubes that makes is uniformly dispersed, and adds 20g 2 then, 2 '-azo two (2, the 4-methyl pentane nitrile), the logical nitrogen deoxygenation of room temperature 25 minutes.Be warming up to 80 ℃ then, react stop after 120 minutes the heating, reduce to room temperature.Isolate the multi-walled carbon nano-tubes of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and use N, dinethylformamide washing 3 times.
In single neck round-bottomed flask of a 100mL, the aqueous sodium hydroxide solution that adds 50mL 2mol/L, the multi-walled carbon nano-tubes that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 90 minutes, after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 3 times, 30 ℃ of dried overnight of vacuum drying oven obtain the multi-walled carbon nano-tubes of carboxyl surface modification.
Embodiment 9: in the 100mL three-necked bottle, add 30mg multi-wall carbon nano-tube pipe powder, add the toluene of 50mL, the ultrasonic multi-walled carbon nano-tubes that makes is uniformly dispersed, and adds 20g 1 then, 1 '-azo two (cyclohexanenitrile), the logical nitrogen deoxygenation of room temperature 30 minutes.Be warming up to 70 ℃ then, react stop after 120 minutes the heating, reduce to room temperature.Isolate the multi-walled carbon nano-tubes of Diisopropyl azodicarboxylate modification with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with toluene wash 3~5 times.
In single neck round-bottomed flask of a 100mL, the aqueous sodium hydroxide solution that adds 50mL 2mol/L, the multi-walled carbon nano-tubes that adds the modification of 50mg Diisopropyl azodicarboxylate then, reflux 2 hours, after reaction finishes, with 0.45um poly(vinylidene fluoride) filtering with microporous membrane, and with deionized water wash 3~5 times, 40 ℃ of dried overnight of vacuum drying oven obtain the multi-walled carbon nano-tubes of carboxyl surface modification.
Claims (7)
1, a kind of preparation method of carbon nano-tube of surface carboxyl modification, it is characterized in that carbon nanotube being carried out surface modification with the azo-initiator of cyano-containing, in acidity or alkaline system, cyano group is hydrolyzed then, thereby obtain the carbon nanotube of surface carboxyl modification, wherein, the control surface carboxyl accounts for the 1-90% of carbon nanotube gross weight.
2, preparation method according to claim 1, it is characterized in that described azo-initiator with cyano-containing is as follows to the step that carbon nanotube carries out modification: with the carbon nanotube ultra-sonic dispersion in coordinative solvent, the azo-initiator that adds cyano-containing then, logical nitrogen 20-40 minute, be warming up to 60-80 ℃, reaction, 90-150 minute; Isolate the azo-initiator modified carbon nanotube of cyano-containing then with filtering with microporous membrane, and wash 3-5 time with coordinative solvent.
3, preparation method according to claim 1, it is characterized in that the described step that cyano group is hydrolyzed is as follows: the azo-initiator modified carbon nanotube of the cyano-containing of gained is added in acidic aqueous solution or the alkaline aqueous solution, backflow 90-150 minute, use filtering with microporous membrane then, isolate carboxy-modified carbon nanotube, and with deionized water wash 3-5 time; At last, put into vacuum drying oven, 35-50 ℃ of drying obtains the carbon nanotube of carboxyl surface modification.
4, preparation method according to claim 2, it is characterized in that used carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, used solvent is toluene, tetrahydrofuran (THF), N, one or more in dinethylformamide, the N-Methyl pyrrolidone.
5, preparation method according to claim 3, the azo-initiator that it is characterized in that used cyano-containing is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two different caprylic nitriles, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 1, one or more in 1 '-azo two (cyclohexanenitrile).
6, preparation method according to claim 3 is characterized in that used acid is one or more in hydrochloric acid, sulfuric acid, the phosphoric acid, and used alkali is one or more in sodium hydroxide, the potassium hydroxide.
7, preparation method according to claim 3 is characterized in that used millipore filtration is PVDF membrane or the poly tetrafluoroethylene of 0.30-0.60 μ m.
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