CN104261385A - Modified carbon material as well as preparation method and application thereof - Google Patents
Modified carbon material as well as preparation method and application thereof Download PDFInfo
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- CN104261385A CN104261385A CN201410496159.7A CN201410496159A CN104261385A CN 104261385 A CN104261385 A CN 104261385A CN 201410496159 A CN201410496159 A CN 201410496159A CN 104261385 A CN104261385 A CN 104261385A
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Abstract
The invention relates to a modified carbon material as well as a preparation method and an application thereof, and belongs to the field of preparation of engineering materials. According to the technical scheme disclosed by the invention, modification of the carbon material comprises the following three steps: acidification of the carbon material; preparation of derivatives of chlorine of the carbon material; and amination of the carbon material. The method can be suitable for carbon materials with different shapes and structures, and the modified carbon material displays a good modification effect when being applied to modification of epoxy resin materials.
Description
Technical field
The present invention relates to a kind of modified carbonaceous components and its preparation method and application, belong to engineering materials preparation field.
Background technology
Epoxy resin refers to the general name of the compounds containing two or more epoxy group(ing) in molecule.Epoxy resin after solidification has the advantages such as cohesive force is strong, high temperature resistant, Corrosion Protection is good, is widely used in the fields such as automobile, navigation, space flight and electrochemistry.But the resin after solidification has the shortcomings such as the low and poorly conductive of toughness, makes its range of application be greatly limited.
Carbon material refers to by single carbon, according to the general name of the class material that the electronic orbit of SP, SP2 or SP3 hydridization forms.It comprises three-dimensional diamond crystal, the various structures such as Graphene, the carbon nanotube of one dimension, the soccerballene of zero dimension of two dimension and the material of form.Carbon material is introduced in epoxy resin-base, while the defect improving its intrinsic poor toughness, the performances such as the thermotolerance, electroconductibility, optical characteristics, radiation hardness characteristic and the chemical-resistant resistance characteristic that also have due to carbon material itself, give the function that gained matrix material is new, be expected to the range of application further expanding epoxide resin material.Therefore the research of carbon material-epoxy resin composite material also becomes the study hotspot in epoxy resin composite material field.
At present, the report about the research at carbon material-epoxy resin composite material is existing a lot, the epoxy resin composite material of particularly carbon nanotube and Graphene modification.But due to carbon nanotube and the intrinsic surface energy of Graphene large, the feature of very easily reuniting, in existing method gained carbon back epoxy resin composite material in, the dispersion state of carbon material is unsatisfactory.Simultaneously due to carbon material with the reason of epoxy resin compatibility difference, in the matrix material of gained, the surface reaction forces of the two is more weak, although some researchs adopt silane coupling agent to carry out modification to it, but due to carbon material surface functional group less, the effect of modified carbon material in modified epoxy is still not ideal enough.
Summary of the invention
The present invention is directed to deficiency of the prior art, propose a kind of novel carbon material method of modifying, this method of modifying is not only applicable to the carbon material of different shape and structure, and modified carbon material shows good modified effect when being applied to epoxide resin material modification.The modification of carbon material described in the technical solution used in the present invention comprises the acidifying of carbon material, the preparation of derivative of the chlorine of carbon material and amination three steps of carbon material.
A preparation method for modified carbonaceous components, comprises following processing step:
1. be that 0.2 ~ 2:100 is placed in reaction soln by carbon material raw material by the mass ratio of carbon material raw material and reaction soln, process 10 ~ 15h at 10 ~ 80 DEG C, washing, wherein, described reaction soln by weight, comprises following component:
The vitriol oil 20
Concentrated nitric acid 1 ~ 5;
2. by step 1. gained material be the solution that 0.1 ~ 0.3:10 is placed in chloride compounds by the mass ratio of carbon material raw material and chloride compounds, 10 ~ 25h is processed at 50 ~ 80 DEG C, washing, the solution of wherein said chloride compounds is by mass ratio for the chloride compounds of 100:1 and DMF form.
3. by step 2. gained material be that 0.1 ~ 0.3g:10mL is placed in amine solvent by the ratio of carbon material raw material and amine solvent, process 15 ~ 25h at 60 DEG C, washing, both.
Carbon material described in the preparation method of modified carbonaceous components of the present invention is carbon nanotube, graphite or diamond powder.Described carbon nanotube more preferably multi-walled carbon nano-tubes; Described graphite more preferably natural flake graphite; Described diamond powder is nano-diamond powder more preferably.
The vitriol oil of the present invention refers to that concentration is not less than the sulfuric acid of 98%, and described concentrated nitric acid refers to that concentration is not less than the nitric acid of 86%.
Preferably, the preferred described step of preparation method of modified carbonaceous components of the present invention 1. in, described reaction soln by weight, is made up of following component:
The vitriol oil 20
Concentrated nitric acid 3 ~ 5.
The preferred described step of preparation method of modified carbonaceous components of the present invention 1. in, described reaction soln by weight, is made up of following component:
The vitriol oil 20
Concentrated nitric acid 1 ~ 5
Oxidation adjuvant 0 ~ 8
Wherein, described oxidation adjuvant is potassium permanganate, Sodium Nitrite or hydrogen peroxide.
Further, the preferred described step of preparation method of modified carbonaceous components of the present invention 1. in, described reaction soln by weight, is made up of following component:
The vitriol oil 20
Concentrated nitric acid 1 ~ 3
Oxidation adjuvant 0 ~ 8.
The method of the invention preferred scheme is: by carbon material raw material by the mass ratio 0.2 ~ 0.5:10 of itself and reaction soln be placed in by the vitriol oil and concentrated nitric acid in mass ratio 20:3 ~ 5 form reaction soln, 10 ~ 13h is reacted at 50 ~ 80 DEG C, washing, wherein, described carbon material is carbon nanotube or diamond powder; And then be the solution that 0.1 ~ 0.2:10 is placed in chloride compounds by the material after washing by the mass ratio of carbon material raw material and chloride compounds, 10 ~ 20h is processed at 50 ~ 70 DEG C, washing, the solution of wherein said chloride compounds is by mass ratio for the chloride compounds of 100:1 and DMF form; Be finally that 0.1 ~ 0.3g:10mL is placed in containing amine solvent by gained material by the ratio of carbon material raw material and amine solvent, process 15 ~ 20h at 60 DEG C, washing, both.
Another preferred scheme of the method for the invention is: be that 0.5 ~ 2:10 puts as in the reaction soln be made up of for 20:1 ~ 3:0 ~ 8 in mass ratio the vitriol oil, concentrated nitric acid and secondary oxidizer by carbon material raw material by the mass ratio of itself and reaction soln, 15 ~ 25h is reacted at 10 ~ 80 DEG C, washing, wherein, described carbon material is graphite; And then be the solution that 0.2 ~ 0.3:10 is placed in chloride compounds by the material after washing by the mass ratio of carbon material raw material and chloride compounds, 15 ~ 25h is processed at 60 ~ 80 DEG C, washing, the solution of wherein said chloride compounds is by mass ratio for the chloride compounds of 100:1 and DMF form; Be finally that 0.1 ~ 0.3g:10mL is placed in containing amine solvent by gained material by the ratio of carbon material raw material and amine solvent, process 20 ~ 25h at 60 DEG C, washing, both.
In technique scheme, described " washing " comprises the step of alcohol wash after washing, pickling, and its object makes the pH value of products therefrom be 7 ± 0.5; Especially, preferred profit uses absolute ethanol washing after being washed with water to neutrality.
In technique scheme, 2. step comprises the step of distillation before described washing step, and its object is the unreacted chloride compounds of distillation, is preferably underpressure distillation.
In technique scheme, 3. step comprises the step of distillation before described washing step, and its object is the unreacted amine solvent of distillation, is preferably underpressure distillation.
Preparation method's preferred steps of modified carbonaceous components of the present invention 2. described chloride compounds is at least one in thionyl chloride, Acetyl Chloride 98Min., Benzoyl chloride, oxalyl chloride, chloroacetyl chloride and trichoroacetic chloride.
Preparation method's preferred steps of modified carbonaceous components of the present invention 3. described amine solvent is quadrol, 1, at least one in 2 propylene diamine, hexanediamine, Isosorbide-5-Nitrae butanediamine, mphenylenediamine, Ursol D and imidazoles.
Another object of the present invention is to provide modified carbonaceous components prepared by aforesaid method.
Another object of the present invention is to provide the application of above-mentioned modified carbonaceous components in preparation reinforced epoxy material.
A preparation method for reinforced epoxy material, be scattered in by above-mentioned modified carbonaceous components in acetone and the ethanol solvent that 1:0 ~ 0.5 is formed by volume, wherein the ratio of modified carbonaceous components and solvent is 10 ~ 80mg:100mL; Mixed with epoxy resin by above-mentioned gained mixing solutions, dispersion, distillation, adds solidifying agent, is cured after mixing, both.
In technique scheme, preferred described epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin.
In technique scheme, 0 ~ 20% (not the comprising 0) that the ratio of preferred mixing solutions and epoxy resin accounts for both mixture total weight amounts by modified carbonaceous components is determined; The amount of preferred described solidifying agent is that 1:1 determines by oxirane value in active hydrogen content in solidifying agent and epoxy resin.
In technique scheme, the object of described distillation removes solvent, is preferably underpressure distillation.
In technique scheme, be cured at described " solidification " is preferable over 30 ~ 180 DEG C; The preferred consolidation time is 4 ~ 24h.
In technique scheme, preferably before being cured, the material mixed is placed in Minton dryer and carries out Fruit storage.
Solidifying agent of the present invention is the solidifying agent that can be used for epoxy resin cure, is preferably 593 solidifying agent, 4,4-diaminodiphenyl-methanes.
Beneficial effect of the present invention is: the method for the invention provides can be applicable to the carbon material processing different shape and structure, has eurytropy; Modified carbon material can be ideal be scattered in resin matrix, avoid the negative impact caused due to the reunion of carbon material; Introduce a large amount of active groups at carbon material surface, carbon material and resin matrix are organically combined with the form of chemical bond, there is therebetween very strong interface interaction power; Solvent for use recoverable in preparation process, preparation cost is lower.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the modified multi-walled carbon nano-tubes of embodiment 2;
Fig. 2 is the scanning electron microscope (SEM) photograph of the modified multi-walled carbon nano-tubes-epoxy resin composite material of embodiment 2 gained.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Test method described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
In following embodiment, the concentration of the vitriol oil used is 98%, the concentration of concentrated nitric acid is 86%, multi-walled carbon nano-tubes wins space high-tech new material technology company limited purchased from Beijing, Nano diamond powder is purchased from the prompt innovative material Science and Technology Ltd. in Xuzhou, and natural flake graphite powder is purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
1. the multi-walled carbon nano-tubes of 200mg is scattered in (mass ratio of the vitriol oil and concentrated nitric acid is 4:1) in the mixing solutions of the 100g vitriol oil and concentrated nitric acid, under the environment of 50 DEG C, 12h is stirred under the rotating speed of 4000r/min, then room temperature is naturally cooled to, with deionized water wash to neutral, then use absolute ethanol washing 3 times.
2. by the carbon nanotube dispersed 1. processed by step of 1.5g in by the thionyl chloride of 50mL and the N of 0.5mL, in the solution of the composition of N-dimethylformamide, gained solution is condensing reflux reaction 20h under the environment of 70 DEG C, after reaction terminates, underpressure distillation removes unreacted thionyl amines, then uses absolute ethanol washing three times.
3. by the carbon nanotube dispersed 2. processed by step of 1.5g in the quadrol of 50mL, solution condensing reflux reaction 20h under the environment of 60 DEG C of gained, after reaction terminates, removes unreacted quadrol, then uses absolute ethanol washing three times.
4. 0.025g is got through the modified carbon nanotube dispersed of above-mentioned steps method process gained in the acetone soln of 5mL, after ultrasonic disperse 20min, joined in the epoxy resin (E51) of the bisphenol A-type of 9.9g, ultrasonic disperse 10min again, then the solidifying agent 593 of 1.98g is added, after mechanical stirring 5min, pour in the mould of preheating at 30 DEG C, then transfer in the baking oven of 30 DEG C, vacuum outgas 30min, then solidifies 24h at ambient pressure and had both obtained the epoxy resin composite material that carbon nanotube mass per-cent is 0.2%.
The shock strength of epoxy resin composite material by the 59.3MPa of virgin resin, be increased to 70.2MPa, breaking tenacity is by the 1.21MPam of virgin resin
1/2, be increased to 2.08MPam
1/2.
Embodiment 2
1. with the step in embodiment 1 1.;
2. with the step in embodiment 1 2.;
3. with the step in embodiment 1 3.;
4. 0.06g is got through the modified carbon nanotube dispersed of above-mentioned steps method process gained in the acetone soln of 5mL, after ultrasonic disperse 20min, joined in the epoxy resin (E51) of the bisphenol A-type of 9.9g, ultrasonic disperse 10min again, then the solidifying agent 593 of 1.98g is added, after mechanical stirring 5min, pour in the mould of preheating at 30 DEG C, then transfer in the baking oven of 30 DEG C, vacuum outgas 30min, then solidifies 24h at ambient pressure and had both obtained the epoxy resin composite material that carbon nanotube mass per-cent is 0.5%.
The shock strength of epoxy resin composite material by the 59.3MPa of virgin resin, be increased to 79.5MPa, breaking tenacity is by the 1.21MPam of virgin resin
1/2, be increased to 2.24MPam
1/2.
Embodiment 3
1. with the step in embodiment 1 1.;
2. with the step in embodiment 1 2.;
3. with the step in embodiment 1 3.;
4. 0.96g is got through the modified carbon nanotube dispersed of above-mentioned steps method process gained in the acetone soln of 5mL, after ultrasonic disperse 20min, joined in the epoxy resin (E51) of the bisphenol A-type of 9.9g, ultrasonic disperse 10min again, then the solidifying agent 593 of 1.98g is added, after mechanical stirring 5min, pour in the mould of preheating at 30 DEG C, then transfer in the baking oven of 30 DEG C, vacuum outgas 30min, then solidifies 24h at ambient pressure and had both obtained the epoxy resin composite material that carbon nanotube mass per-cent is 0.8%.
The shock strength of epoxy resin composite material by the 59.3MPa of virgin resin, be increased to 84.2MPa, breaking tenacity is by the 1.21MPam of virgin resin
1/2, be increased to 2.36MPam
1/2.
Embodiment 4
1. under ice-water bath condition, 1.5g natural flake graphite powder, 3.5g concentrated nitric acid are joined in the 70g vitriol oil, after Homogeneous phase mixing, 10 DEG C, under the agitation condition of 4000r/min rotating speed, slowly add 9g potassium permanganate in 2h, temperature rises to 30 DEG C of reaction 10h afterwards.Be warmed up to 80 DEG C after dropwise adding 100mL distilled water again, continue reaction 2h.Reaction terminates the hydrogen peroxide process of 30% of rear 30mL, then with dilute hydrochloric acid and distilled water cleaning several, until pH value reaches the 50 DEG C of dryings of 7 ± 0.5 vacuum, obtains graphene oxide.
2. the graphene oxide of 1g is scattered in the N of thionyl chloride by 50mL and 0.5mL, in the solution of N-dimethylformamide composition, solution condensing reflux reaction 24h under the environment of 70 DEG C of gained, after reaction terminates, underpressure distillation removes unreacted thionyl amines, then absolute ethanol washing three times.
3. be scattered in the quadrol of 50mL by the graphene oxide 2. processed by step of 1g, solution condensing reflux reaction 24h under the environment of 60 DEG C of gained, after reaction terminates, removes unreacted quadrol, then uses absolute ethanol washing three times.
4. 0.025g is got through the modified graphene dispersion of above-mentioned steps method process gained in the acetone soln of 5mL, after ultrasonic disperse 20min, joined in the epoxy resin (E51) of the bisphenol A-type of 9.9g, ultrasonic disperse 10min again, then the solidifying agent 593 of 1.98g is added, after mechanical stirring 5min, pour in the mould of preheating at 30 DEG C, then transfer in the baking oven of 30 DEG C, vacuum outgas 30min, finally solidifying the mass percent that 24h both obtained Graphene is at ambient pressure the epoxy resin composite material of 0.2%.
The shock strength of epoxy resin composite material by the 59.3MPa of virgin resin, be increased to 80.2MPa.
Embodiment 5
1. the Nano diamond powder of 200mg is scattered in (mass ratio of the vitriol oil and concentrated nitric acid is 3:1) in the mixing solutions of the 100g vitriol oil and concentrated nitric acid, under the environment of 50 DEG C, 12h is stirred under the rotating speed of 4000r/min, then room temperature is naturally cooled to, with deionized water wash to neutral, then use absolute ethanol washing 3 times.
2. the Nano diamond 1. processed by step of 1.5g is scattered in the N of thionyl chloride by 50mL and 0.5mL, in the solution of N-dimethylformamide composition, solution condensing reflux reaction 24h under the environment of 70 DEG C of gained, after reaction terminates, underpressure distillation removes unreacted thionyl amines, then absolute ethanol washing three times.
3. be scattered in the quadrol of 50mL by the Nano diamond 2. processed by step of 1.5g, solution condensing reflux reaction 24h under the environment of 60 DEG C of gained, after reaction terminates, removes unreacted quadrol, then absolute ethanol washing three times.
4. getting 0.9g is scattered in the acetone soln of 5mL through the Nano diamond that above-mentioned steps method process gained is modified, after ultrasonic disperse 20min, joined in the epoxy resin (E828) of the bisphenol A-type of 9.9g, ultrasonic disperse 10min again, then 593 solidifying agent of 1.1g are added, after mechanical stirring 5min, pour in the mould of preheating at 30 DEG C, then transfer in the baking oven of 30 DEG C, vacuum outgas 30min, finally solidifying the mass percent that 24h both obtained Nano diamond is at ambient pressure the epoxy resin composite material of 7%.
The hardness of epoxy resin composite material by the 0.4MPa of virgin resin, be increased to 68.2MPa, Young's modulus, by the 0.27GPa of virgin resin, is increased to 3.2GPa.
Claims (8)
1. a preparation method for modified carbonaceous components, comprises following processing step:
1. be that 0.2 ~ 2:100 is placed in reaction soln by carbon material raw material by the mass ratio of carbon material raw material and reaction soln, process 10 ~ 15h at 10 ~ 80 DEG C, washing, wherein, described reaction soln by weight, comprises following component:
The vitriol oil 20
Concentrated nitric acid 1 ~ 5;
2. by step 1. gained material be the solution that 0.1 ~ 0.3:10 is placed in chloride compounds by the mass ratio of carbon material raw material and chloride compounds, 10 ~ 25h is processed at 50 ~ 80 DEG C, washing, the solution of wherein said chloride compounds is by mass ratio for the chloride compounds of 100:1 and DMF form.
3. by step 2. gained material be that 0.1 ~ 0.3g:10mL is placed in amine solvent by the ratio of carbon material raw material and amine solvent, process 15 ~ 25h at 60 DEG C, washing, both.
2. method according to claim 1, is characterized in that: described chloride compounds is at least one in thionyl chloride, Acetyl Chloride 98Min., Benzoyl chloride, oxalyl chloride, chloroacetyl chloride and trichoroacetic chloride.
3. method according to claim 1, is characterized in that: described amine solvent is quadrol, 1, at least one in 2 propylene diamine, hexanediamine, Isosorbide-5-Nitrae butanediamine, mphenylenediamine, Ursol D and imidazoles.
4. method according to claim 1, is characterized in that: described step 1. in, described reaction soln by weight, is made up of following component:
The vitriol oil 20
Concentrated nitric acid 1 ~ 5
Oxidation adjuvant 0 ~ 8
Wherein, described oxidation adjuvant is potassium permanganate, Sodium Nitrite or hydrogen peroxide.
5. method according to claim 1, is characterized in that: comprise following processing step:
1. be that 0.2 ~ 0.5:10 is placed in reaction soln by carbon material raw material by the mass ratio of itself and reaction soln, react 10 ~ 13h at 50 ~ 80 DEG C, washing, wherein, described carbon material is carbon nanotube or diamond powder, and described reaction soln by weight, is made up of following component:
The vitriol oil 20
Concentrated nitric acid 3 ~ 5;
2. by step 1. gained material be the solution that 0.1 ~ 0.2:10 is placed in chloride compounds by the mass ratio of carbon material raw material and chloride compounds, 10 ~ 20h is processed at 50 ~ 70 DEG C, washing, the solution of wherein said chloride compounds is by mass ratio for the chloride compounds of 100:1 and DMF form;
3. by step 2. gained material be that 0.1 ~ 0.3g:10mL is placed in amine solvent by the ratio of carbon material raw material and amine solvent, process 15 ~ 20h at 60 DEG C, washing, both.
6. method according to claim 4, is characterized in that: comprise following processing step:
1. be that 0.5 ~ 2:10 is placed in reaction soln by carbon material raw material by the mass ratio of itself and reaction soln, react 15 ~ 25h at 10 ~ 80 DEG C, washing, wherein, described carbon material is graphite, and described reaction soln by weight, is made up of following component:
The vitriol oil 20
Concentrated nitric acid 1 ~ 3
Oxidation adjuvant 0 ~ 8;
2. by step 1. gained material be the solution that 0.2 ~ 0.3:10 is placed in chloride compounds by the mass ratio of carbon material raw material and chloride compounds, 15 ~ 25h is processed at 60 ~ 80 DEG C, washing, the solution of wherein said chloride compounds is by mass ratio for the chloride compounds of 100:1 and DMF form;
3. by step 2. gained material be that 0.1 ~ 0.3g:10mL is placed in amine solvent by the ratio of carbon material raw material and amine solvent, process 20 ~ 25h at 60 DEG C, washing, both.
7. the modified carbonaceous components prepared by the method described in any one of claim 1 ~ 6.
8. a preparation method for reinforced epoxy material, is characterized in that: be scattered in by claim 7 gained modified carbonaceous components in acetone and the ethanol solvent that 1:0 ~ 0.5 is formed by volume, wherein the ratio of modified carbonaceous components and solvent is 10 ~ 80mg:100mL; Mixed with epoxy resin by above-mentioned gained mixing solutions, dispersion, distillation, adds solidifying agent, is cured after mixing, both.
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| CN109148847A (en) * | 2018-08-07 | 2019-01-04 | 湖州创亚动力电池材料有限公司 | A kind of the hard carbon cladding negative electrode material and its liquid phase preparation process of the boron doping modification with high rate capability |
| WO2020042295A1 (en) * | 2018-08-31 | 2020-03-05 | 华中师范大学 | Preparation method for monodispersed aminated nano-diamond colloid solution, secondary dispersion process therefor, and application thereof in cell labeling |
| US11105811B2 (en) | 2018-08-31 | 2021-08-31 | Central China Normal University | Preparation method and secondary dispersion of monodisperse aminated manodiamond colloid solution and its application in cellular biomarking |
| WO2020082297A1 (en) * | 2018-10-25 | 2020-04-30 | 苏州吉人高新材料股份有限公司 | Composite water-based epoxy resin and manufacturing method therefor |
| CN115093656A (en) * | 2022-07-11 | 2022-09-23 | 广东铭宸工贸有限公司 | Wear-resistant modified PVC material and synthesis process |
| CN115093656B (en) * | 2022-07-11 | 2023-10-13 | 广东铭宸工贸有限公司 | Wear-resistant modified PVC material and synthesis process thereof |
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