CN101037198A - Carbon nano tube with high water-solubility and preparation method thereof - Google Patents
Carbon nano tube with high water-solubility and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a high water soluble carbon nanotube and a preparation method of the same. In the present invention, the carbon nanotube experiences noncovalent bond combinative coating modification by using the pi-pi conjugation between the hydrolysis styrene-maleic anhydride copolymer and the carbon nanotube; the dispersion stability of the carbon nanotube in water is improved by using the carboxylic acid anion with good water solubility of the copolymers; so that the water solubility of the carbon nanotube is greatly improved. The water solubility carbon nanotube coated by hydrolysis styrene-maleic anhydride copolymer is obtained by using hydrolysis styrene-maleic anhydride copolymer, carbon nanotube and water as raw material, adopting a circular fashion to inject hydrolysis styrene-maleic anhydride copolymers, and using an ultra sonic dispersion method and centrifugal method. The present invention has the advantages of that the technology is simple, the obtained water solubility carbon nanotube has a solubility of 29.2 mg/ml and an excellent stability, and the styrene-maleic anhydride copolymer has a simple preparation process and a lower cost, so that the large scale preparation and the industrial application of the water solubility carbon nanotube can be greatly improved.
Description
Technical field
The present invention relates to a kind of carbon nano tube with high water-solubility and preparation method thereof, relate in particular to a kind of highly water-soluble carbon nanotube of using polymer overmold and preparation method thereof.
Background technology
Carbon nanotube has caused that with its particular structure and good light, electricity, magnetic and mechanical property scientific circles and industry member pay close attention to widely, but, very poor water-soluble of carbon nanotube is one of bottleneck that limits its scale operation and application, especially in biological field and environment-friendly material field.Therefore, people have proposed several different methods and have improved the water-soluble of carbon nanotube, wherein a kind of method is exactly by various chemical modification methods the sidewall of carbon nanotube or port to be carried out covalent linkage to derive, realize that its dissolving disperses or effectively peels off, and perhaps adopts violent treatment process such as long-time acidifying oxidation, microwave-assisted oxidation to obtain water-soluble carbon nanometer tube.Though yet this method solubleness is good, the charge stripping efficiency height, thus the perfect structure of meeting destroying carbon nanometer tube itself influences its various premium propertiess, and complex disposal process is difficult to control; Another kind of is with various non covalent bond modifying method, by small molecules tensio-active agent or amphipathic nature polyalcohol carbon nanotube is wrapped up and to realize that its dissolving disperses and peels off, these class methods are little to the damage of carbon nanotube, basically can keep its original performance, but often have that solubleness is little, poor stability and charge stripping efficiency be low, the more high shortcoming of employed tensio-active agent or polymer concentration.
People such as the Smally of the U.S. (Chemical Physics Letters, 2001, Vol.342 p265) utilizes polymer overmold Single Walled Carbon Nanotube such as polyacetylene alkene pyrrolidone or sulfonated polystyrene, has obtained the water-soluble mono wall carbon nano tube; People such as the Kotov of the U.S. (Journal of the American Chemical Society, 2005, Vol.127, p3463) utilize the coated single-walled and multi-walled carbon nano-tubes of multipolymer of N-hexadecyl-4-vinylpridine bromination ammonium salt, N-ethyl-4-vinylpridine bromination ammonium salt and 4-vinylpridine, obtain the carbon nano-tube aqueous solutions of stably dispersing, but do not see the solubleness report of above-mentioned water-soluble carbon nanometer tube.The people such as Hu Shengshui (CN 1699155A) of China utilize the azoic dyestuff enveloped carbon nanometer tube, and the solubleness of the water-soluble carbon nanometer tube that obtains is 3.5mg/mL.People such as American I slam (Nano Letters, 2003, Vol.3 p269) utilize water-soluble carbon nanometer tube solubleness that the Sodium dodecylbenzene sulfonate enveloped carbon nanometer tube obtains up to 20mg/mL, but its surfactant content that adopts is 10 times of carbon nanotube weight.Therefore, how to obtain the carbon nanotube of high water soluble and keep its perfect structure and specific performance and the least possible chemical reagent that adds remains a great challenge.
Summary of the invention
The purpose of this invention is to provide a kind of carbon nano tube with high water-solubility and preparation method thereof.
Carbon nano tube with high water-solubility is formed by hydrolysis styrene-maleic anhydride copolymer enveloped carbon nanometer tube, and the weight ratio of carbon nanotube and hydrolysis styrene-maleic anhydride copolymer is 1: 10～10: 1.
The preparation method of carbon nano tube with high water-solubility comprises the steps:
(1) by weight 1 part of carbon nanotube being joined in 50～400 parts of aqueous solution that contain 0.05～2wt% hydrolysis polystyrene-maleic anhydride multipolymer, then mixed solution was carried out ultra-sonic dispersion 1～4 hour;
(2) the ultra-sonic dispersion liquid that obtains is carried out centrifugation, centrifugal rotational speed is 3000～20000RPM, and centrifugation time is 5～60 minutes;
(3) precipitation of centrifugation gained is joined 50～400 parts and contain in 0.05～2wt% hydrolysis polystyrene-maleic anhydride aqueous copolymers solution, then mixed solution was carried out ultra-sonic dispersion 30～120 minutes; The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 3000～20000RPM, and centrifugation time is 5～60 minutes, collects upper strata centrifugate;
(4) step (3) is repeated 2～10 times;
(5) the upper strata centrifugate of combining step (3) and step (4) gained, ultrafiltration is collected filter cake and is carried out drying, gets the highly water-soluble carbon nanotube that the hydrolysis styrene-maleic anhydride copolymer coats.
Carbon nanotube is single wall, double-walled or multi-walled carbon nano-tubes.
Carbon nanotube also can be a modified carbon nano-tube.
The modified carbon nano-tube treatment process is: with the carbon nanotube of 1 weight part, with 100～1000 parts of aqueous solution that contain 0.05～2mol/L superoxide, ultra-sonic dispersion 10～60 minutes added 10～300 parts of vitriol oils, 30 ℃～100 ℃ following stir process 5～48 hours; Treatment solution is carried out centrifugal, centrifugal rotational speed is 3000～20000RPM, and centrifugation time is 5～60 minutes; The throw out thin up, carry out again behind the ultra-sonic dispersion centrifugal, dilution so repeatedly, ultra-sonic dispersion and centrifugal till centrifugate is neutrality; Dry black solid at last and precipitate the carbon nanotube that obtains peroxide treatment.
Superoxide is K
2S
2O
8, Na
2S
2O
8, (NH)
2S
2O
8Or H
2O
2Hydrolysis polystyrene-maleic anhydride multipolymer is that number-average molecular weight (Mn) is 1000～150000 with the alternating copolymerization of alkali lye processing or the hydrolysate of random copolymerization phenylethylene-maleic anhydride.
The present invention since the oxidisability of the acidic treatment liquid of superoxide relatively a little less than, agraphitic carbon oxidized degree with respect to carbon nanotube is bigger under this condition, therefore, in carrying out ultra-sonic dispersion, centrifugal process, help removing agraphitic carbon impurity, be further purified carbon nanotube.In addition, the hydrolysis styrene-maleic anhydride copolymer is good macromolecule dispersing agent, can effectively further remove agraphitic carbon impurity in the ultra-sonic dispersion centrifugal process its first time in water-soluble carbon nanometer tube preparation of the present invention, guaranteed the high purity of gained water-soluble carbon nanometer tube.The inventive method technology is simple, and condition is controlled easily, can effectively promote the mass preparation and the industrial application of this water-soluble carbon nanometer tube.
Description of drawings
Fig. 1 is K
2S
2O
8Multi-walled carbon nano-tubes (the K that handles
2S
2O
8-treated MWNT), the multi-walled carbon nano-tubes (HSMA-MWNTs) of hydrolysis polystyrene-maleic anhydride multipolymer coating and the thermogravimetric analysis figure of hydrolysis styrene-maleic anhydride copolymer (HSMA).Work atmosphere is N
2Protection, heat-up rate is 10 ℃/min.
Fig. 2 (A) is K
2S
2O
8Handle multi-walled carbon nano-tubes transmission electron microscope picture;
Fig. 2 (B) and Fig. 2 (C) are hydrolysis phenylethylene-maleic anhydride polymer overmold multi-walled carbon nano-tubes transmission electron microscope pictures;
Fig. 2 (D) left side K
2S
2O
8Handle multi-walled carbon nano-tubes dispersive photo in water, Fig. 2 (D) the right is the aqueous solution (29.2mg/ml) picture of hydrolysis phenylethylene-maleic anhydride polymer overmold multi-walled carbon nano-tubes.
Embodiment
The present invention is based on the π-πGong Ezuoyong that utilizes hydrolysis polystyrene-maleic anhydride multipolymer and carbon nanotube carbon nanotube is carried out the non covalent bond modification and utilizes the carboxylate anion who has good aqueous solubility on the hydrolysis polystyrene-maleic anhydride polymkeric substance to improve the dispersion stabilization of carbon nanotube in water, thereby improve the water miscible method of carbon nanotube.The carbon nanotube of this method preparation not only has the characteristics of highly water-soluble and high charge stripping efficiency, the low damage feature that also has the non-covalent modification method, and this method technology is simple, with low cost, helps promoting the mass preparation and the industrial application of water-soluble carbon nanometer tube.
Embodiment 1
The 100mg multi-walled carbon nano-tubes is added 75ml contain 0.2mol/L K
2S
2O
8The aqueous solution in, ultra-sonic dispersion is after 30 minutes, add 12.5ml 98% vitriol oil after, stirred 24 hours down at 60 ℃.Treatment solution was carried out 16000 RPM centrifugal 15 minutes, the precipitation thin up, carry out again behind the ultra-sonic dispersion centrifugal, dilution precipitation so repeatedly, ultra-sonic dispersion, carry out centrifugal, till solution is neutrality.Dry the black solid precipitation at last and obtain K
2S
2O
8The multi-walled carbon nano-tubes of handling.
Embodiment 2
The 100mg Single Walled Carbon Nanotube is added 75ml contain 0.2mol/L K
2S
2O
8The aqueous solution in, ultra-sonic dispersion is after 30 minutes, add 12.5ml 98% vitriol oil after, stirred 24 hours down at 60 ℃.Treatment solution was carried out 16000RPM centrifugal 15 minutes, the precipitation thin up, carry out again behind the ultra-sonic dispersion centrifugal, dilution precipitation so repeatedly, ultra-sonic dispersion, carry out centrifugal, till solution is neutrality.Dry the black solid precipitation at last and obtain K
2S
2O
8The Single Walled Carbon Nanotube of handling.
Embodiment 3
Get 50mg K
2S
2O
8The multi-walled carbon nano-tubes of handling joins in hydrolysis styrene-maleic anhydride copolymer (Mn=23360) aqueous solution of 50ml 0.1wt.%, then mixed solution is carried out ultra-sonic dispersion 2 hours.
The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 16000RPM, and centrifugation time is 15 minutes.Discard supernatant liquid, the precipitation of centrifugation gained is added in the hydrolysis styrene-maleic anhydride copolymer aqueous solution of 50ml 0.1wt.%, then mixed solution was carried out ultra-sonic dispersion 60 minutes.The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 16000RPM, and centrifugation time is 15 minutes, collects upper strata centrifugate.The precipitation of gained is joined in the hydrolysis styrene-maleic anhydride copolymer aqueous solution of 50ml 0.1wt.% and repeat ultra-sonic dispersion 60 minutes, 16000RPM centrifugal 15 minutes, so circulates 9 times.Collect the upper strata centrifugate of 9 circulation gained and carry out 0.22 μ m membrane filtration, solid is carried out drying, get the multi-walled carbon nano-tubes that the hydrolysis styrene-maleic anhydride copolymer coats.
Embodiment 4
Get 50mg K
2S
2O
8Handle Single Walled Carbon Nanotube, join in hydrolysis styrene-maleic anhydride copolymer (Mn=23360) aqueous solution of 50ml 0.1wt.%, then mixed solution was carried out ultra-sonic dispersion 2 hours.The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 16000RPM, and centrifugation time is 15 minutes.Discard supernatant liquid, the precipitation of centrifugation gained is joined in the hydrolysis styrene-maleic anhydride copolymer aqueous solution of 50ml 0.1wt.%, then mixed solution was carried out ultra-sonic dispersion 60 minutes.The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 16000RPM, and centrifugation time is 15 minutes, collects upper strata centrifugate.The precipitation of gained is added in the hydrolysis styrene-maleic anhydride copolymer aqueous solution of 50ml 0.1wt.% and repeat ultra-sonic dispersion 60 minutes, 16000RPM centrifugal 15 minutes, so circulates 9 times.Collect the upper strata centrifugate of 9 circulation gained and carry out 0.22 μ m membrane filtration, solid is carried out drying, get the Single Walled Carbon Nanotube that the hydrolysis styrene-maleic anhydride copolymer coats.
Embodiment 5
Get 50mg K
2S
2O
8Handle multi-walled carbon nano-tubes, join in hydrolysis styrene-maleic anhydride copolymer (Mn=53493) aqueous solution of 60ml 0.15wt.%, then mixed solution was carried out ultra-sonic dispersion 1 hour.The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 10000RPM, and centrifugation time is 20 minutes.Discard supernatant liquid, the precipitation of centrifugation gained is added in the hydrolysis styrene-maleic anhydride copolymer aqueous solution of 60ml 0.15wt.%, then mixed solution was carried out ultra-sonic dispersion 45 minutes.The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 10000RPM, and centrifugation time is 20 minutes, collects upper strata centrifugate.The precipitation of gained is joined in the hydrolysis styrene-maleic anhydride copolymer aqueous solution of 60ml 0.15wt.% and repeat ultra-sonic dispersion 45 minutes, 10000RPM centrifugal 20 minutes, so circulates 6 times.Collect the upper strata centrifugate of 6 circulation gained and carry out 0.35 μ m membrane filtration, solid is carried out drying, get the multi-walled carbon nano-tubes that the hydrolysis styrene-maleic anhydride copolymer coats.
Embodiment 6
Get 50mg K
2S
2O
8Handle Single Walled Carbon Nanotube, join in hydrolysis styrene-maleic anhydride copolymer (Mn=53493) aqueous solution of 60ml 0.15wt.%, then mixed solution was carried out ultra-sonic dispersion 1 hour.The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 10000RPM, and centrifugation time is 20 minutes.Discard supernatant liquid, the precipitation of centrifugation gained is joined in the hydrolysis styrene-maleic anhydride copolymer aqueous solution of 60ml 0.15wt.%, then mixed solution was carried out ultra-sonic dispersion 45 minutes.The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 10000RPM, and centrifugation time is 20 minutes, collects upper strata centrifugate.The precipitation of gained is added in the hydrolysis styrene-maleic anhydride copolymer aqueous solution of 60ml 0.15wt.% and repeat ultra-sonic dispersion 45 minutes, 10000RPM centrifugal 20 minutes, so circulates 6 times.Collect the upper strata centrifugate of 6 circulation gained and carry out 0.35 μ m membrane filtration, solid is carried out drying, get the Single Walled Carbon Nanotube that the hydrolysis styrene-maleic anhydride copolymer coats.
Below in conjunction with accompanying drawing 1 and Fig. 2 the excellent heat stability of the water-soluble multi-wall carbon nanotube that hydrolysis styrene-maleic anhydride copolymer provided by the present invention coats and the good solubility property in water thereof are described.Fig. 1 is K
2S
2O
8The multi-walled carbon nano-tubes that the multi-walled carbon nano-tubes of handling, hydrolysis polystyrene-maleic anhydride multipolymer (Mn=23360) coat and the thermogravimetric analysis figure of hydrolysis styrene-maleic anhydride copolymer.As can be seen from the figure, the thermostability of the multi-walled carbon nano-tubes of hydrolysis phenylethylene-maleic anhydride polymer overmold illustrates that up to 400 ℃ the present invention has avoided the destruction to carbon nanotube structure.Thermogravimetic analysis (TGA) according to Fig. 1, the content that can calculate the polymkeric substance in the multi-walled carbon nano-tubes that this hydrolysis styrene-maleic anhydride copolymer coats is 57%, the weight ratio that is polymkeric substance and carbon nanotube was significantly less than other polymkeric substance or the dosage of surfactant of bibliographical information near 1: 1.
Can obviously find out K from Fig. 2 (A) with (B)
2S
2O
8The multi-walled carbon nano-tubes smooth surface of handling, and hydrolysis styrene-maleic anhydride copolymer coating multi-walled carbon nano-tubes is obviously wrapped up by the unformed material of one deck, it has confirmed the coating effect of hydrolysis styrene-maleic anhydride copolymer to carbon nanotube, and from Fig. 2 (C) multi-walled carbon nano-tubes favorable dispersity of coating of hydrolysis styrene-maleic anhydride copolymer as can be seen.Fig. 2 (D) left side multi-walled carbon nano-tubes as can be seen is insoluble in water, and Fig. 2 (D) the right has shown that the multi-walled carbon nano-tubes that the hydrolysis styrene-maleic anhydride copolymer coats has higher solvability, and this stability of solution is very good, deposits and does not see obvious layering in 5 months yet.
The solubleness test of this water-soluble multi-wall carbon nanotube is as follows: the multi-walled carbon nano-tubes that 200mg hydrolysis styrene-maleic anhydride copolymer is coated joins in the 6ml deionized water ultra-sonic dispersion 1 hour.After dispersion liquid left standstill 3 days, carefully take out supernatant liquid 2ml, place baking oven to remove moisture, put it into the oven dry of spending the night in 80 ℃ of vacuum drying ovens then, weigh with syringe.The solubleness of calculating this water-soluble multi-wall carbon nanotube is 29.2mg/ml.
Claims (7)
1. a carbon nano tube with high water-solubility is characterized in that, it is formed by hydrolysis styrene-maleic anhydride copolymer enveloped carbon nanometer tube, and the weight ratio of carbon nanotube and hydrolysis styrene-maleic anhydride copolymer is 1: 10～10: 1.
2. the preparation method of carbon nano tube with high water-solubility according to claim 1 is characterized in that comprising the steps:
(1) by weight 1 part of carbon nanotube being joined in 50～400 parts of aqueous solution that contain 0.05～2wt% hydrolysis polystyrene-maleic anhydride multipolymer, then mixed solution was carried out ultra-sonic dispersion 1～4 hour;
(2) the ultra-sonic dispersion liquid that obtains is carried out centrifugation, centrifugal rotational speed is 3000～20000RPM, and centrifugation time is 5～60 minutes;
(3) precipitation of centrifugation gained is joined 50～400 parts and contain in 0.05～2wt% hydrolysis polystyrene-maleic anhydride aqueous copolymers solution, then mixed solution was carried out ultra-sonic dispersion 30～120 minutes; The ultra-sonic dispersion liquid that obtains is carried out centrifugation, and centrifugal rotational speed is 3000～20000RPM, and centrifugation time is 5～60 minutes, collects upper strata centrifugate;
(4) step (3) is repeated 2～10 times;
(5) the upper strata centrifugate of combining step (3) and step (4) gained, ultrafiltration is collected filter cake and is carried out drying, gets the highly water-soluble carbon nanotube that the hydrolysis styrene-maleic anhydride copolymer coats.
3. the preparation method of a kind of carbon nano tube with high water-solubility according to claim 2 is characterized in that described carbon nanotube is single wall, double-walled or multi-walled carbon nano-tubes.
4. the preparation method of a kind of carbon nano tube with high water-solubility according to claim 2 is characterized in that described carbon nanotube is a modified carbon nano-tube.
5. the preparation method of a kind of carbon nano tube with high water-solubility according to claim 4, it is characterized in that described modified carbon nano-tube treatment process is: with the carbon nanotube of 1 weight part, with 100～1000 parts of aqueous solution that contain 0.05～2mol/L superoxide, ultra-sonic dispersion 10～60 minutes, add 10～300 parts of vitriol oils, 30 ℃～100 ℃ following stir process 5～48 hours; Treatment solution is carried out centrifugal, centrifugal rotational speed is 3000～20000RPM, and centrifugation time is 5～60 minutes; The throw out thin up, carry out again behind the ultra-sonic dispersion centrifugal, dilution so repeatedly, ultra-sonic dispersion and centrifugal till centrifugate is neutrality; Dry black solid at last and precipitate the carbon nanotube that obtains peroxide treatment.
6. the preparation method of a kind of carbon nano tube with high water-solubility according to claim 5 is characterized in that described superoxide is K
2S
2O
8, Na
2S
2O
8, (NH)
2S
2O
8Or H
2O
2
7. the preparation method of a kind of carbon nano tube with high water-solubility according to claim 2, it is characterized in that described hydrolysis polystyrene-maleic anhydride multipolymer is that number-average molecular weight (Mn) is 1000～150000 with the alternating copolymerization of alkali lye processing or the hydrolysate of random copolymerization phenylethylene-maleic anhydride.
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| CN101792633A (en) * | 2010-03-09 | 2010-08-04 | 浙江大学 | Preparation method for antistatic super hydrophobic composite coating |
| CN102500255A (en) * | 2011-10-31 | 2012-06-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano tube dispersing method |
| CN102515142A (en) * | 2011-12-19 | 2012-06-27 | 上海交通大学 | Method for purification of low-purity single-wall carbon nano-tubes |
| CN101780379B (en) * | 2009-12-10 | 2012-08-01 | 安徽金阳纳米科技有限公司 | High-concentration carbon nano tube water dispersoid and preparation method thereof |
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| CN101780379B (en) * | 2009-12-10 | 2012-08-01 | 安徽金阳纳米科技有限公司 | High-concentration carbon nano tube water dispersoid and preparation method thereof |
| CN101792633A (en) * | 2010-03-09 | 2010-08-04 | 浙江大学 | Preparation method for antistatic super hydrophobic composite coating |
| CN102500255A (en) * | 2011-10-31 | 2012-06-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano tube dispersing method |
| CN102515142A (en) * | 2011-12-19 | 2012-06-27 | 上海交通大学 | Method for purification of low-purity single-wall carbon nano-tubes |
| CN110896144A (en) * | 2018-09-12 | 2020-03-20 | 深圳新宙邦科技股份有限公司 | Conductive composition, battery pole piece and battery |
| CN110896144B (en) * | 2018-09-12 | 2021-11-09 | 深圳新宙邦科技股份有限公司 | Conductive composition, battery pole piece and battery |
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