CN100357346C - Process for preparing multifunctional carbon nanotube for epoxy resin nano composites - Google Patents
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Abstract
The present invention more specifically relates to a preparation method for a multifunctional carbon nanometer tube for epoxy resin nanometer composite materials, which belongs to the technical field of nanometer materials. The preparation method adopts the molecular design conception. After the surface of a purified carbon nanometer tube is quantitatively carboxylated and chloridized, long chain diamine with a character structure is introduced so as to a graft type carbon nanometer tube with quantitative active amino groups on the surface. The affinity of the structure for basal body resin and the chemical reaction of the basal body resin are used, and thereby, the dispersivity of the carbon nanometer tube is improved. The adhesive strength of the carbon nanometer tube and the basal surface of the basal body resin are improved, and simultaneously, the carbon nanometer tube performs the functions of dispersion, good interface adhesion, intensification, solidification, etc. Thus, the epoxy resin nanometer composite materials prepared by the preparation method use a multifunctional carbon nanometer tube, and the preparation method is favorable to the improvement of the integral performance of carbon nanometer tube / epoxy resin composite materials, and is suitable for the industrial application of the carbon nanometer tube.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of multifunctional carbon nanotube for epoxy resin nano composites.
Background technology
Carbon nanotube (CNTs) since being found by Japanese scholar Iijima in 1991, with its distinctive mechanics, electricity and chemical property and unique accurate one dimension tracheary element structure and the many potential using value that in following high-tech area, is had, become the research focus of chemistry, physics and material science rapidly.
CNTs has very big length-to-diameter ratio, generally greater than 1000.The Young's modulus of CNTs is identical with diamond, and theoretical strength can reach 1.0TPa, is 100 times of steel; The calculated value of carbon nanotube tensile strength is up to 177GPa, far above carbon fiber (2GPa～5GPa), whisker (20GPa) and high-strength steel (1GPa～2GPa).The axial Young's modulus experimental value of multi-walled carbon nano-tubes is 200GPa～4000GPa, and axial bending intensity is 14GPa, and axial compression strength is 100GPa, and has the toughness (theoretical maximum unit elongation can reach 20%) of superelevation, and density only is 1/7 of steel.Therefore carbon nanotube is considered to ultimate fortifying fibre, is expected to become the ideal enhancing body and the functive of advanced composite material.
Want the good carbon nano-tube/polymer composite material of processability, importantly carbon nanotube disperses in matrix fully, and creation good interface, make between itself and matrix and have good cohesive force, like this could be to carbon nanotube with load transfer, do not slide and the surface does not take place, play the enhanced effect.But because the CNTs surface energy is high, Van der Waals force effect greatly makes it assemble bunchy easily between the tube and tube, and be dissolved in any solvent hardly, therefore be difficult to be distributed in matrices of composite material or the various application system, this is the bottleneck that the restriction carbon nanotube is used.Therefore existing preparation technology can't prepare nano composite material truly, because 1. carbon nanotube does not reach the nano level homodisperse in polymkeric substance; 2. the interface of polymkeric substance and carbon nanotube lacks chemical b `, and the biphase boundary strength is low.Therefore, existing polymer/carbon nano-tube performance of composites is far below desired value.
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of easy dispersion, interface adhesion are good, strengthen the multifunctional carbon nanotube for epoxy resin nano composites that solidifies function.
The preparation method of the multifunctional carbon nanotube for epoxy resin nano composites of proposition of the present invention, with the carbon nano tube surface purifying, carbon nano tube surface behind the purifying is carried out quantitatively carboxylated, after carrying out chloride again, introducing has the long-chain diamine of feature structure, obtains the graft type carbon nanotube that the surface has quantitative active amino.Its concrete steps are as follows:
(1) carbon nanotube 1 weight part and mineral acid 10～150 weight parts are mixed, under 0～100kHz ultrasonic wave, reacted 0.1～100 hour, be heated to 20～100 ℃ then, stirring and back flow reaction 0.1～100 hour, with the microfiltration membrane suction filtration, washing is to neutral, and vacuum-drying is 5～48 hours under 20～200 ℃ of temperature, obtains the carbon nanotube of purifying;
(2) 1 weight part and acid with strong oxidizing property 10～150 weight parts that obtain purifying carbon nano-tube in the step (1) are mixed, with 0～100kHz ultrasonication 0.1～100 hour, be heated to 20～100 ℃ then, stirring and back flow reaction 0.1～100 hour, the ultra-filtration membrane suction filtration, repetitive scrubbing repeatedly is neutral to solution, and vacuum-drying is 5～48 hours under 20～200 ℃ of temperature, obtains the acidifying carbon nanotube;
(3) add step (2) gained surface quantitatively carbon nanotube 1 weight part and chloride reagent 1～100 weight part of carboxyl, with 0～100kHz ultrasonication after 10～1000 minutes, be heated to 20～100 ℃, stir, back flow reaction 1～100 hour, suction filtration, repetitive scrubbing is removed chloride reagent, obtains the carbon nanotube of chloride;
(4) add step (3) gained chloride carbon nanotube 1 weight part and polyamine 1～50 weight part, with 0～100kHz ultrasonication 5～1200 minutes, under 20～200 ℃ of temperature, reacted 1～100 hour then, suction filtration, repetitive scrubbing, vacuum-drying is 1～24 hour under 0～180 ℃ of temperature, obtains the graft type carbon nanotube that the surface has active amino.
Among the present invention, carbon nanotube described in step (1) or (2) is the single wall or the multi-walled carbon nano-tubes of arc discharge method, chemical Vapor deposition process and the preparation of laser evaporation method.
Among the present invention, mineral acid described in the step (1) be in the hydrochloric acid of the sulfuric acid of nitric acid, 1～50% weight acid concentration of 1～30% weight acid concentration or 0.1～40% weight acid concentration any.
Among the present invention, acid with strong oxidizing property described in the step (2) be in 0.1～70% weight acid concentration nitric acid, 20～100% weight acid concentration sulfuric acid, 1/100～100/1 mol ratio concentrated nitric acid and vitriol oil mixing solutions or 10～90% weight concentration superoxols etc. any.
Among the present invention, acyl chlorinating agent described in the step (3) be in sulfur oxychloride, phosphorus trichloride or the phosphorus pentachloride etc. any.
Among the present invention, the polyamine that has feature structure described in the step (4) comprises chlorination hexanediamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines, 13 carbon diamines, N, in N-dimethyl dipropyl triamine, tetraethylene pentamine or the polyethylene polyamine etc. any.
Among the present invention, the quantitative analysis of carboxyl-content in the acidifying carbon nanotube can be adopted TGA, XPS or nuclear magnetic resonance method in the step (2).
Preparation method provided by the invention is simple, has the characteristics of controllability and quantification; The surface of gained has the carbon nanotube of the graft type of a large amount of amino, owing to have a large amount of long-chain fat hydrocarbyl groups, shows good dispersiveness in Resins, epoxy and organic solvent, has improved the workability of carbon nanotube greatly; The quantitative amino in surface can produce chemical reaction with Resins, epoxy, has increased the boundary strength between matrix resin and the strongthener on the one hand, has solidified Resins, epoxy on the other hand; The carbon nanotube of the particular procedure that is added can give full play of the enhancing characteristic of high-performance carbon nanotube because good dispersion and interface bond, for the industrialization of producing the high-performance nano matrix material provides new approach.
The present invention adopts the thought of molecular designing, quantitatively introduce long-chain polyamine in carbon nano tube surface with feature structure, utilize this structure to the avidity of matrix resin and with the chemical reaction of matrix resin, thereby improve the dispersiveness of carbon nanotube, improve the interface binding intensity of itself and matrix resin, thereby make carbon nanotube play multiple functions such as easy dispersion, interface adhesion are good, enhancing, curing simultaneously.The multifunctional carbon nanotube for epoxy resin nano composites of the present invention's preparation, carbon nanotube through the modification of quantification special surface, multiple functions such as easy dispersion, interface adhesion are good, enhancing, curing have been given, so more help improving the overall performance of carbon nano tube compound material, be convenient to the industrial application of carbon nanotube.Therefore, the high-performance nano matrix material has important science and technology value and actual application value with the development of multifunctional carbon nanotube.
Description of drawings
Fig. 1 is a kind of multifunctional carbon nanotube for epoxy resin nano composites transmission electron microscope picture.
Fig. 2 is a kind of multifunctional carbon nanotube for epoxy resin nano composites XPS figure.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: with the multi-walled carbon nano-tubes of chemical Vapor deposition process preparation (OD＜8nm) be an initial raw material, pass through purifying, acidifying, chloride after, connect 12 carbon diamines after, then obtain the graft type carbon nanotube that ten diamines are contained on the surface.
Step (1): in the single neck round-bottomed flask of churned mechanically 250ml is housed, add 2g multi-walled carbon nano-tubes raw material and 100mL, 20% weight concentration salpeter solution, under the 40kHz ultrasonic wave, handled 24 hours, be heated to 50 ℃ then, reacted 30 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.45 μ m, with deionized water wash 3-6 time to neutrality, 80 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 24 hours;
Step (2): in the single neck round-bottomed flask of the 250mL that the magnetic agitation rotor is housed, the carbon nanometer tube material 2g and the 100mL that add the purifying that obtains in the step (1), 60% weight concentration concentrated nitric acid, with 3 minutes post-heating to 100 of 40kHz ultrasonication ℃, stir the reaction down 12 hours that also refluxes, with the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtration of 0.22 μ m, with deionized water repetitive scrubbing 3-6 time neutrality extremely, 80 ℃ of vacuum-dryings obtained carboxylic acidifying carbon nanotube after 24 hours;
Step (3): in the 250ml three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (2) gained acidifying carbon nanotube 1.5g and thionyl chloride 8g, with the 40Hz ultrasonication after 30 minutes, be heated to 60 ℃, the stirring and the reaction down 24 hours that refluxes, suction filtration and repetitive scrubbing are removed thionyl chloride, obtain the carbon nanotube of chloride;
Step (4): in the 250mI three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (3) gained acidylate carbon nanotube 1.3g and 12 carbon diamine 25g, with the 40kHz ultrasonication after 30 minutes, reacted 24 hours down at 100 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, after using deionized water wash 3-5 time repeatedly, 80 ℃ of vacuum-drying 18 hours obtains the surface and has amino carbon nanotube;
Fig. 1 has provided the surface and has had amino graft type multi-walled carbon nano-tubes transmission electron microscope picture, and carbon nanotube is enclosed with the polymkeric substance of one deck light color as can be seen.
It is 5.0% (with the mol ratio of carbon) that the XPS data that provide from Fig. 2 can draw multi-wall carbon nano-tube tube-surface carboxyl-content.Therefore can calculate and handle back multi-walled carbon nano-tubes surface amino groups content is 5.0%.
Embodiment 2: (OD＜8nm) be an initial raw material, after purifying, acidifying, chloride, connects N, and N-dimethyl dipropyl triamine then obtains the Single Walled Carbon Nanotube that the surface has the graft type of amino with the Single Walled Carbon Nanotube of arc discharge method preparation.
Step (1): in the single neck round-bottomed flask of churned mechanically 250ml is housed, add 1g Single Walled Carbon Nanotube raw material and 200mL, the sulfuric acid of 30% weight concentration, with 80kHz ultrasonication 12 hours, be heated to 80 ℃ then, reacted 10 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.45 μ m, to neutral, 100 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 18 hours with the deionized water repetitive scrubbing;
Step (2): in the single neck round-bottomed flask of the 250mL that the magnetic agitation rotor is housed, the carbon nanometer tube material 1.5g and the 150ml that add the purifying that obtains in the step (1), 98% vitriol oil mixing solutions, with 60 minutes post-heating to 60 of 80kHz ultrasonication ℃, stir the reaction down 36 hours that also refluxes, with the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtration of 0.22 μ m, with deionized water repetitive scrubbing 4-6 time neutrality extremely, 100 ℃ of vacuum-dryings obtained carboxylic acidifying carbon nanotube after 24 hours;
Step (3): in the 250ml three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (2) gained acidifying carbon nanotube 1.0g and phosphorus trichloride 12g, with the 100Hz ultrasonication after 30 minutes, be heated to 100 ℃, the stirring and the reaction down 48 hours that refluxes, suction filtration and repetitive scrubbing are removed phosphorus trichloride, obtain the carbon nanotube of chloride;
Step (4): in the 250mI three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (3) gained acidylate carbon nanotube 1.3g and N, N-dimethyl dipropyl triamine 25g, with the 80kHz ultrasonication after 30 minutes, reacted 12 hours down at 100 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, repeatedly with behind the deionized water wash, 120 ℃ of vacuum-drying 10 hours obtains the surface and has amino carbon nanotube;
XPS result shows that Single Walled Carbon Nanotube surface amino groups content is 5.5%.
Embodiment 3: (OD＜8nm) be an initial raw material, after purifying, acidifying, chloride, connects 12 carbon diamines, then obtains the multi-walled carbon nano-tubes that the surface has the graft type of amino with the multi-walled carbon nano-tubes of laser evaporation method preparation.
Step (1): in the single neck round-bottomed flask of churned mechanically 250ml is housed, add 1g multi-walled carbon nano-tubes raw material and 100mL20% weight concentration sulphuric acid soln, with 80kHz ultrasonication 10 hours, heating and stir and reflux then at 80-90 ℃, reacted 10 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of 0.45 μ m, to neutrality, 100 ℃ of vacuum-dryings obtain the carbon nanotube of purifying after 24 hours with deionized water repetitive scrubbing 3-5 time;
Step (2): in the single neck round-bottomed flask of the 250mL that the magnetic agitation rotor is housed, the carbon nanometer tube material and the 100ml that add the 2g purifying, 3/1 the concentrated nitric acid and the vitriol oil, with 100 minutes post-heating to 120 of 20kHz ultrasonication ℃, the stirring and the reaction down 12 hours that refluxes with the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtration of 0.22 μ m, use the deionized water repetitive scrubbing repeatedly to neutral, 120 ℃ of vacuum-dryings obtained carboxylic acidifying carbon nanotube after 48 hours;
Step (3): in the 250ml three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (1) gained acidifying carbon nanotube 1.5g and phosphorus pentachloride 20g, with the 20Hz ultrasonication after 120 minutes, be heated to 80 ℃, the stirring and the reaction down 24 hours that refluxes, suction filtration and repetitive scrubbing are removed phosphorus pentachloride, obtain the carbon nanotube of chloride;
Step (4): in the 250mI three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (3) gained acidylate carbon nanotube 1.3g and tetraethylene pentamine 25g, with the 20kHz ultrasonication after 80 minutes, reacted 18 hours down at 120 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, repeatedly with behind the deionized water wash, 150 ℃ of vacuum-drying 3 hours obtains the surface and has amino carbon nanotube;
XPS analysis result shows that multi-walled carbon nano-tubes surface amino groups content is 7.0%.
Claims (5)
1, the preparation method of multifunctional carbon nanotube for epoxy resin nano composites is characterized in that concrete steps are as follows:
(1) carbon nanotube 1 weight part and mineral acid 10～150 weight parts are mixed, under 0～100kHz ultrasonic wave, reacted 0.1～100 hour, be heated to 20～100 ℃ then, reacted 0.1～100 hour, with the microfiltration membrane suction filtration, washing is to neutral, and vacuum-drying is 5～48 hours under 20～200 ℃ of temperature, obtains the carbon nanotube of purifying;
(2) 1 weight part and acid with strong oxidizing property 10～150 weight parts that obtain purifying carbon nano-tube in the step (1) are mixed, with 0～100kHz ultrasonication 0.1～100 hour, be heated to 20～100 ℃ then, stirring and back flow reaction 0.1～100 hour, the ultra-filtration membrane suction filtration, repetitive scrubbing repeatedly is neutral to solution, and vacuum-drying is 5～48 hours under 20～200 ℃ of temperature, obtains the acidifying carbon nanotube;
(3) add step (2) gained surface quantitatively carbon nanotube 1 weight part and chloride reagent 1～100 weight part of carboxyl, with 0～100kHz ultrasonication after 10～1000 minutes, be heated to 20～100 ℃, stir, back flow reaction 1～100 hour, suction filtration, chloride reagent is removed in washing, obtains the carbon nanotube of chloride;
(4) add step (3) gained chloride carbon nanotube 1 weight part and polyamine 1～50 weight part, with 0～100kHz ultrasonication 5～1200 minutes, under 20～200 ℃ of temperature, reacted 1～100 hour then, suction filtration, repetitive scrubbing, vacuum-drying is 1～24 hour under 0～180 ℃ of temperature, obtains the graft type carbon nanotube that the surface has active amino; Wherein, described polyamine is chlorination hexanediamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines, 13 carbon diamines, N, in N-dimethyl dipropyl triamine, tetraethylene pentamine or the polyethylene polyamine any.
2, the preparation method of multifunctional carbon nanotube for epoxy resin nano composites according to claim 1 is characterized in that carbon nanotube is single wall or multi-walled carbon nano-tubes described in the step (1).
3, the preparation method of multifunctional carbon nanotube for epoxy resin nano composites according to claim 1, it is characterized in that mineral acid described in the step (1) be in the hydrochloric acid of the sulfuric acid of nitric acid, 1～50% weight acid concentration of 1～30% weight acid concentration or 0.1～40% weight acid concentration any.
4, the preparation method of multifunctional carbon nanotube for epoxy resin nano composites according to claim 1, it is characterized in that acid with strong oxidizing property described in the step (2) be in 0.1～70% weight acid concentration nitric acid, 20～100% weight acid concentration sulfuric acid, 1/100～100/1 mol ratio concentrated nitric acid and vitriol oil mixing solutions or 10～90% weight concentration superoxols any.
5, the preparation method of multifunctional carbon nanotube for epoxy resin nano composites according to claim 1, it is characterized in that acyl chlorinating agent described in the step (3) be in sulfur oxychloride, phosphorus trichloride or the phosphorus pentachloride any.
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| CN101407620B (en) * | 2007-10-11 | 2011-05-25 | 同济大学 | High performance epoxy resins composite material and preparation thereof |
| CN101407622B (en) * | 2007-10-11 | 2012-03-21 | 同济大学 | Carbon nano-tube / unsaturated polyester composite material and preparation thereof |
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| CN103951940A (en) * | 2014-04-10 | 2014-07-30 | 惠州学院 | Antistatic epoxy resin composite material and preparation method thereof |
| CN104087224B (en) * | 2014-07-10 | 2016-06-22 | 北京中煤矿山工程有限公司 | A kind of carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement |
| CN106684045B (en) * | 2016-12-22 | 2019-01-11 | 江苏师范大学 | A kind of carbon nanotube reinforced insulation heat-conducting resin and preparation method thereof |
| CN108586809B (en) * | 2018-05-16 | 2019-08-09 | 西北工业大学 | A kind of carbon nanotube base compounded mix and preparation method thereof and a kind of epoxy resin base electro-magnetic screen nanocomposite |
| CN110615427B (en) * | 2018-06-19 | 2021-01-05 | 哈尔滨工业大学 | Preparation method of high-flexibility self-crosslinking carbon nanotube film |
| CN112029240B (en) * | 2020-09-07 | 2023-05-16 | 吉祥三宝高科纺织有限公司 | High-heat-conductivity polymer carbon nano tube composite material and preparation method thereof |
| CN114381092A (en) * | 2021-07-30 | 2022-04-22 | 江苏博泓新材料科技有限公司 | High-temperature thickening vinyl resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486999A (en) * | 2003-07-31 | 2004-04-07 | 上海交通大学 | Prepn process of in-situ polymerized polymer grafted carbon nanotube |
| CN1544322A (en) * | 2003-11-27 | 2004-11-10 | 上海交通大学 | Carbon nanometer tube with initiating group on surface and its preparation method |
| CN1562738A (en) * | 2004-04-15 | 2005-01-12 | 上海交通大学 | Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method |
-
2006
- 2006-03-14 CN CNB2006100246755A patent/CN100357346C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486999A (en) * | 2003-07-31 | 2004-04-07 | 上海交通大学 | Prepn process of in-situ polymerized polymer grafted carbon nanotube |
| CN1544322A (en) * | 2003-11-27 | 2004-11-10 | 上海交通大学 | Carbon nanometer tube with initiating group on surface and its preparation method |
| CN1562738A (en) * | 2004-04-15 | 2005-01-12 | 上海交通大学 | Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method |
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