CN104261385B - A kind of modified carbonaceous components and its preparation method and application - Google Patents
A kind of modified carbonaceous components and its preparation method and application Download PDFInfo
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- CN104261385B CN104261385B CN201410496159.7A CN201410496159A CN104261385B CN 104261385 B CN104261385 B CN 104261385B CN 201410496159 A CN201410496159 A CN 201410496159A CN 104261385 B CN104261385 B CN 104261385B
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Abstract
The present invention relates to a kind of modified carbonaceous components and its preparation method and application, belong to engineering material preparation field.The modification of material with carbon element described in the technical solution used in the present invention includes the preparation of the derivative of the chlorine of the acidifying of material with carbon element, material with carbon element and three steps of amination of material with carbon element.The method is not only applicable to the material with carbon element of different shape and structure, and modified material with carbon element shows good modified effect when being applied to epoxide resin material modification.
Description
Technical field
The present invention relates to a kind of modified carbonaceous components and its preparation method and application, belong to engineering material preparation field.
Background technology
Epoxy resin refers to the general name of the compounds in molecule containing two or more epoxy radicals.After solidification
Epoxy resin has the advantages such as cohesive force is strong, high temperature resistant, Corrosion Protection is good, be widely used in automobile, navigation,
The field such as space flight and electrochemistry.But the resin after Gu Hua has that toughness is low and the shortcoming such as poorly conductive so that it is range of application
It is greatly limited.
Material with carbon element refers to by single carbon, the class material formed according to the electron orbit of SP, SP2 or SP3 hydridization
The general name of material.It includes the diamond crystal of three-dimensional, the Graphene of two dimension, one-dimensional CNT, the fowler of zero dimension
The various structures such as alkene and the material of form.Material with carbon element is introduced in epoxy resin-base, improving its intrinsic poor toughness
Defect while, due also to material with carbon element itself had heat resistance, electric conductivity, optical characteristics, radiation hardness characteristic
With the performance such as chemical-resistant resistance characteristic, give the function that gained composite is new, be expected to further expand epoxy resin material
The range of application of material.Therefore the research of material with carbon element-epoxy resin composite material also becomes epoxy resin composite material field
Study hotspot.
Report currently, with respect to the research at material with carbon element-epoxy resin composite material is a lot, particularly CNT
The epoxy resin composite material modified with Graphene.The surface intrinsic yet with CNT and Graphene can be big,
The feature easily reunited, in existing method in the carbon back epoxy resin composite material of gained, the dispersity of material with carbon element is also
Undesirable.Simultaneously because the reason poor with epoxy resin compatibility of material with carbon element, in the composite of gained the two
Surface reaction forces is more weak, although some researchs use silane coupler it to be carried out modification, yet with material with carbon element table
The less reason of face functional group, modified material with carbon element effect in terms of modified epoxy is the most not ideal enough.
Summary of the invention
The present invention is directed to deficiency of the prior art, it is proposed that a kind of novel material with carbon element method of modifying, this modification side
Method is not only applicable to the material with carbon element of different shape and structure, and modified material with carbon element is being applied to epoxy resin material
Material shows good modified effect time modified.The modification of material with carbon element described in the technical solution used in the present invention includes carbon material
Acidifying, the preparation of the derivative of the chlorine of material with carbon element and three steps of amination of material with carbon element expected.
A kind of preparation method of modified carbonaceous components, including following processing step:
1. it is 0.2～2:100 to be placed in reaction solution by material with carbon element raw material by the mass ratio of material with carbon element raw material Yu reaction solution
In, at 10～80 DEG C process 10～15h, washing, wherein, described reaction solution by weight, including following component:
The concentrated sulfuric acid 20
Red fuming nitric acid (RFNA) 1～5；
2. it is 0.1～0.3:10 to be placed in acyl by step 1. gained material by the mass ratio of material with carbon element raw material Yu chloride compounds
In the solution of chlorine compound, processing 10～25h at 50～80 DEG C, washing, the solution of wherein said chloride compounds is by pressing
Mass ratio is chloride compounds and the N of 100:1, and N-dimethylformamide forms.
3. it is that 0.1～0.3g:10mL to be placed in amine molten by step 2. gained material by the ratio of material with carbon element raw material and amine solvent
In agent, process 15～25h at 60 DEG C, wash, both.
Material with carbon element described in the preparation method of modified carbonaceous components of the present invention is CNT, graphite or diamond dust.
Described CNT more preferably multi-walled carbon nano-tubes；Described graphite more preferably natural flake graphite；Institute
State diamond dust more preferably nano-diamond powder.
The concentrated sulfuric acid of the present invention refers to that the sulfuric acid that concentration is not less than 98%, described red fuming nitric acid (RFNA) refer to the nitre that concentration is not less than 86%
Acid.
Preferably, the preferred described step of preparation method of modified carbonaceous components of the present invention 1. in, described reaction solution is pressed
Weight portion, is made up of following component:
The concentrated sulfuric acid 20
Red fuming nitric acid (RFNA) 3～5.
The preferred described step of preparation method of modified carbonaceous components of the present invention 1. in, described reaction solution by weight,
It is made up of following component:
The concentrated sulfuric acid 20
Red fuming nitric acid (RFNA) 1～5
Oxidation adjuvant 0～8
Wherein, described oxidation adjuvant is potassium permanganate, natrium nitrosum or hydrogen peroxide.
Further, the preferred described step of preparation method of modified carbonaceous components of the present invention 1. in, described reaction solution
By weight, it is made up of following component:
The concentrated sulfuric acid 20
Red fuming nitric acid (RFNA) 1～3
Oxidation adjuvant 0～8.
One preferred scheme of the method for the invention is: by material with carbon element raw material by itself and the mass ratio of reaction solution
0.2～0.5:10 be placed in by the concentrated sulfuric acid and red fuming nitric acid (RFNA) 20:3 in mass ratio～5 form reaction solution in, at 50～80 DEG C
Reaction 10～13h, washing, wherein, described material with carbon element is CNT or diamond dust；After washing the most again
Material be 0.1～0.2:10 to be placed in the solution of chloride compounds by the mass ratio of material with carbon element raw material Yu chloride compounds,
Processing 10～20h at 50～70 DEG C, washing, the solution of wherein said chloride compounds is by the acyl being 100:1 in mass ratio
Chlorine compound and N, N-dimethylformamide forms；By gained material by the ratio of material with carbon element raw material and amine solvent it is finally
0.1～0.3g:10mL is placed in containing in amine solvent, processes 15～20h, wash at 60 DEG C, both.
Another preferred scheme of the method for the invention is: by material with carbon element raw material by its mass ratio with reaction solution be
0.5～2:10 to put the reaction as being made up of for 20:1～3:0～8 in mass ratio the concentrated sulfuric acid, red fuming nitric acid (RFNA) and cooxidant molten
In liquid, reacting 15～25h at 10～80 DEG C, washing, wherein, described material with carbon element is graphite；After washing the most again
Material be 0.2～0.3:10 to be placed in the solution of chloride compounds by the mass ratio of material with carbon element raw material Yu chloride compounds,
Processing 15～25h at 60～80 DEG C, washing, the solution of wherein said chloride compounds is by the acyl being 100:1 in mass ratio
Chlorine compound and N, N-dimethylformamide forms；By gained material by the ratio of material with carbon element raw material and amine solvent it is finally
0.1～0.3g:10mL is placed in containing in amine solvent, processes 20～25h, wash at 60 DEG C, both.
In technique scheme, described " washing " includes washing, the step that alcohol is washed after pickling, and its purpose makes gained
The pH value of product is 7 ± 0.5；In particular it is preferred to profit uses absolute ethanol washing after being washed with water to neutrality.
In technique scheme, including the step of distillation before the most described washing step of step, its purpose is distillation unreacted
Chloride compounds, distillation of preferably reducing pressure.
In technique scheme, including the step of distillation before the most described washing step of step, its purpose is distillation unreacted
Amine solvent, distillation of preferably reducing pressure.
The most described chloride compounds of preparation method preferred steps of modified carbonaceous components of the present invention is thionyl chloride, acetyl
At least one in chlorine, chlorobenzoyl chloride, oxalyl chloride, chloracetyl chloride and trichloro-acetic chloride.
The most described amine solvent of preparation method preferred steps of modified carbonaceous components of the present invention be ethylenediamine, 1,2 the third two
At least one in amine, hexamethylene diamine, 1,4 butanediamine, m-phenylene diamine (MPD), p-phenylenediamine and imidazoles.
It is a further object of the present invention to provide modified carbonaceous components prepared by said method.
It is yet another object of the invention to provide the application in preparation reinforced epoxy material of the above-mentioned modified carbonaceous components.
The preparation method of a kind of reinforced epoxy material, is scattered in acetone and ethanol by volume by above-mentioned modified carbonaceous components
Ratio is in the solvent that 1:0～0.5 is formed, and wherein the ratio of modified carbonaceous components and solvent is 10～80mg:100mL；By above-mentioned institute
Obtain mixed solution to mix with epoxy resin, dispersion, distillation, add curing agent, solidify after mixing, both.
In technique scheme, the most described epoxy resin be bisphenol A type epoxy resin, bisphenol f type epoxy resin,
Bisphenol-s epoxy resin.
In technique scheme, preferably to account for both mixtures by modified carbonaceous components total for mixed solution and the ratio of epoxy resin
The 0 of weight～20% (not including 0) determine；The amount of the most described curing agent presses active hydrogen content and epoxy in curing agent
In resin, epoxide number is that 1:1 determines.
In technique scheme, the purpose of described distillation is to remove solvent, distillation of preferably reducing pressure.
In technique scheme, described " solidification " is preferable at 30～180 DEG C and solidifies；The preferred consolidation time is
4～24h.
In technique scheme, preferably before solidifying, it is placed in Minton dryer by the material mixed
Row Fruit storage.
Curing agent of the present invention is the curing agent that can be used for epoxy resin cure, preferably 593 curing agent, 4,4-diamino
Base diphenyl methane.
The invention have the benefit that the present invention provides method to can be applicable to process different shape and the material with carbon element of structure,
There is eurytopicity；Modified material with carbon element can be ideal be scattered in resin matrix, it is to avoid due to the group of material with carbon element
The negative effect gathered and cause；Substantial amounts of active group is introduced so that material with carbon element and resin matrix at carbon material surface
Organically combine with the form of chemical bond, there is therebetween the strongest interface interaction power；In preparation process, solvent for use can
Recycling, preparation cost is relatively low.
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.
Detailed description of the invention
Following non-limiting example can make those of ordinary skill in the art that the present invention be more fully understood, but not with
Any mode limits the present invention.
Test method described in following embodiment, if no special instructions, is conventional method；Described reagent and material,
If no special instructions, the most commercially obtain.
In following embodiment, the concentration of the concentrated sulfuric acid used is 98%, and the concentration of red fuming nitric acid (RFNA) is 86%, and multi-walled carbon nano-tubes is purchased
Win space high-tech new material technology Co., Ltd from Beijing, Nano diamond powder is limited purchased from Xuzhou victory innovative material science and technology
Company, 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 the (concentrated sulfuric acid in the mixed solution of the 100g concentrated sulfuric acid and red fuming nitric acid (RFNA)
It is 4:1 with the mass ratio of red fuming nitric acid (RFNA)), in the environment of 50 DEG C, stir 12h under the rotating speed of 4000r/min, then certainly
So it is cooled to room temperature, is washed with deionized to neutrality, then use absolute ethanol washing 3 times.
2. the CNT 1. processed by step of 1.5g is scattered in the thionyl chloride by 50mL and 0.5mL
In the solution of the composition of DMF, gained solution is condensing reflux reaction 20h in the environment of 70 DEG C,
After reaction terminates, decompression is distilled off unreacted thionyl amines, then uses absolute ethanol washing three times.
3. being scattered in the ethylenediamine of 50mL by the CNT 2. processed by step of 1.5g, the solution of gained exists
In the environment of 60 DEG C, condensing reflux reaction 20h, after reaction terminates, removes unreacted ethylenediamine, then uses anhydrous second
Alcohol washs three times.
4. take 0.025g to process the modified CNT of gained through above-mentioned steps method to be scattered in the acetone of 5mL molten
In liquid, after ultrasonic disperse 20min, add it in the epoxy resin (E51) of the bisphenol A-type of 9.9g, then surpass
Sound dispersion 10min, is subsequently adding the curing agent 593 of 1.98g, after mechanical agitation 5min, pours at 30 DEG C pre-
In the mould of heat, it is then transferred in the baking oven of 30 DEG C, vacuum outgas 30min, solidifies 24h the most at ambient pressure
Both the epoxy resin composite material that carbon nanotube mass percentage is 0.2% had been obtained.
The impact strength of epoxy resin composite material by the 59.3MPa of pure resin, increase to 70.2MPa, fracture
Intensity is by the 1.21MPa m of pure resin1/2, increase to 2.08MPa m1/2。
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. take 0.06g and be scattered in the acetone soln of 5mL through the CNT that above-mentioned steps method process gained is modified
In, after ultrasonic disperse 20min, add it in the epoxy resin (E51) of the bisphenol A-type of 9.9g, more ultrasonic
Dispersion 10min, is subsequently adding the curing agent 593 of 1.98g, after mechanical agitation 5min, pours into and preheats at 30 DEG C
Mould in, be then transferred in the baking oven of 30 DEG C, vacuum outgas 30min, the most at ambient pressure solidification 24h both
Obtain the epoxy resin composite material that carbon nanotube mass percentage is 0.5%.
The impact strength of epoxy resin composite material by the 59.3MPa of pure resin, increase to 79.5MPa, fracture
Intensity is by the 1.21MPa m of pure resin1/2, increase to 2.24MPa m1/2。
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. take 0.96g and be scattered in the acetone soln of 5mL through the CNT that above-mentioned steps method process gained is modified
In, after ultrasonic disperse 20min, add it in the epoxy resin (E51) of the bisphenol A-type of 9.9g, more ultrasonic
Dispersion 10min, is subsequently adding the curing agent 593 of 1.98g, after mechanical agitation 5min, pours into and preheats at 30 DEG C
Mould in, be then transferred in the baking oven of 30 DEG C, vacuum outgas 30min, the most at ambient pressure solidification 24h both
Obtain the epoxy resin composite material that carbon nanotube mass percentage is 0.8%.
The impact strength of epoxy resin composite material by the 59.3MPa of pure resin, increase to 84.2MPa, fracture
Intensity is by the 1.21MPa m of pure resin1/2, increase to 2.36MPa m1/2。
Embodiment 4
1., under the conditions of ice-water bath, 1.5g natural flake graphite powder, 3.5g red fuming nitric acid (RFNA) are joined in the 70g concentrated sulfuric acid,
Uniformly after mixing, 10 DEG C, under the stirring condition of 4000r/min rotating speed, in 2h, be slowly added to 9g potassium permanganate,
Temperature rises to 30 DEG C of reaction 10h afterwards.It is warmed up to 80 DEG C after being added dropwise over 100mL distilled water again, continues reaction
2h.Reaction processes with the hydrogen peroxide of the 30% of 30mL after terminating, and then cleans for several times with watery hydrochloric acid and distilled water,
Until pH value reaches 50 DEG C of 7 ± 0.5 vacuum and is dried, obtain graphene oxide.
2. the graphene oxide of 1g is scattered in the thionyl chloride by 50mL and the N of 0.5mL, N dimethyl formyl
In the solution of amine composition, the solution of gained is condensing reflux reaction 24h in the environment of 70 DEG C, after reaction terminates, subtracts
Pressure is distilled off unreacted thionyl amines, then absolute ethanol washing three times.
3. the graphene oxide 2. processed by step of 1g is scattered in the ethylenediamine of 50mL, the solution of gained
In the environment of 60 DEG C, condensing reflux reaction 24h, after reaction terminates, removes unreacted ethylenediamine, then uses nothing
Water-ethanol washs three times.
4. take 0.025g and process the modified graphene dispersion of gained in the acetone soln of 5mL through above-mentioned steps method
In, after ultrasonic disperse 20min, add it in the epoxy resin (E51) of the bisphenol A-type of 9.9g, more ultrasonic
Dispersion 10min, is subsequently adding the curing agent 593 of 1.98g, after mechanical agitation 5min, pours into and preheats at 30 DEG C
Mould in, be then transferred in the baking oven of 30 DEG C, vacuum outgas 30min, the most at ambient pressure solidification 24h both
Obtain the epoxy resin composite material that mass percent is 0.2% of Graphene.
The impact strength of epoxy resin composite material by the 59.3MPa of pure resin, increase to 80.2MPa.
Embodiment 5
1. the Nano diamond powder of 200mg is scattered in (dense sulphur in the mixed solution of the 100g concentrated sulfuric acid and red fuming nitric acid (RFNA)
The mass ratio of acid and red fuming nitric acid (RFNA) is 3:1), in the environment of 50 DEG C, stir 12h under the rotating speed of 4000r/min, then
Naturally cool to room temperature, be washed with deionized to neutrality, then use absolute ethanol washing 3 times.
2. the Nano diamond 1. processed by step of 1.5g is scattered in the thionyl chloride by 50mL and 0.5mL
DMF composition solution in, the solution of gained in the environment of 70 DEG C condensing reflux reaction 24h,
After reaction terminates, decompression is distilled off unreacted thionyl amines, then absolute ethanol washing three times.
3. the Nano diamond 2. processed by step of 1.5g is scattered in the ethylenediamine of 50mL, gained molten
Liquid is condensing reflux reaction 24h in the environment of 60 DEG C, after reaction terminates, removes unreacted ethylenediamine, then without
Water-ethanol washs three times.
4. take 0.9g to process the modified Nano diamond of gained through above-mentioned steps method to be scattered in the acetone of 5mL molten
In liquid, after ultrasonic disperse 20min, add it in the epoxy resin (E828) of the bisphenol A-type of 9.9g, then
Ultrasonic disperse 10min, is subsequently adding 593 curing agent of 1.1g, after mechanical agitation 5min, pours at 30 DEG C
In the mould of preheating, it is then transferred in the baking oven of 30 DEG C, vacuum outgas 30min, solidifies 24h the most at ambient pressure
Both the epoxy resin composite material that mass percent is 7% of Nano diamond had been obtained.
The hardness of epoxy resin composite material by the 0.4MPa of pure resin, increase to 68.2MPa, Young's modulus
By the 0.27GPa of pure resin, increase to 3.2GPa.
Claims (8)
1. a preparation method for modified carbonaceous components, including following processing step:
1. be 0.2～2:100 to be placed in material with carbon element raw material in reaction solution by the mass ratio of material with carbon element raw material Yu reaction solution, at 10～80 DEG C, process 10～15h, washing, wherein, described reaction solution by weight, including following component:
The concentrated sulfuric acid 20
Red fuming nitric acid (RFNA) 1～5；
2. it is 0.1～0.3:10 to be placed in step 1. gained material in the solution of chloride compounds by the mass ratio of material with carbon element raw material Yu chloride compounds, 10～25h are processed at 50～80 DEG C, washing, the solution of wherein said chloride compounds is by forming for the chloride compounds of 100:1 and DMF in mass ratio；
3. it is 0.1～0.3g:10mL to be placed in step 2. gained material in amine solvent by the ratio of material with carbon element raw material and amine solvent, at 60 DEG C, processes 15～25h, washing, i.e.
?.
Method the most according to claim 1, it is characterised in that: described chloride compounds is at least one in thionyl chloride, chloroacetic chloride, chlorobenzoyl chloride, oxalyl chloride, chloracetyl chloride and trichloro-acetic chloride.
Method the most according to claim 1, it is characterised in that: described amine solvent be ethylenediamine, 1, at least one in 2-propane diamine, hexamethylene diamine, Putriscine, m-phenylene diamine (MPD), p-phenylenediamine and imidazoles.
Method the most according to claim 1, it is characterised in that: described step 1. in, described reaction solution by weight, is made up of following component:
The concentrated sulfuric acid 20
Red fuming nitric acid (RFNA) 1～5
Oxidation adjuvant 0～8
Wherein, described oxidation adjuvant is potassium permanganate, natrium nitrosum or hydrogen peroxide.
Method the most according to claim 1, it is characterised in that: include following processing step:
1. it is 0.2～2:100 to be placed in material with carbon element raw material in reaction solution by its mass ratio with reaction solution, reacts 10～13h at 50～80 DEG C, washing, wherein, described material with carbon element is CNT or diamond dust, and described reaction solution by weight, is made up of following component:
The concentrated sulfuric acid 20
Red fuming nitric acid (RFNA) 3～5；
2. it is 0.1～0.2:10 to be placed in step 1. gained material in the solution of chloride compounds by the mass ratio of material with carbon element raw material Yu chloride compounds, 10～20h are processed at 50～70 DEG C, washing, the solution of wherein said chloride compounds is by forming for the chloride compounds of 100:1 and DMF in mass ratio；
3. it is 0.1～0.3g:10mL to be placed in step 2. gained material in amine solvent by the ratio of material with carbon element raw material and amine solvent, at 60 DEG C, processes 15～20h, washing, i.e.
?.
Method the most according to claim 4, it is characterised in that: include following processing step:
1. it is 0.2～2:100 to be placed in material with carbon element raw material in reaction solution by its mass ratio with reaction solution, at 10～80 DEG C, reacts 10～15h, washing, wherein, described material with carbon element is graphite, and described reaction solution by weight, is made up of following component:
The concentrated sulfuric acid 20
Red fuming nitric acid (RFNA) 1～3
Oxidation adjuvant 0～8；
2. it is 0.2～0.3:10 to be placed in step 1. gained material in the solution of chloride compounds by the mass ratio of material with carbon element raw material Yu chloride compounds, 15～25h are processed at 60～80 DEG C, washing, the solution of wherein said chloride compounds is by forming for the chloride compounds of 100:1 and DMF in mass ratio；
3. it is 0.1～0.3g:10mL to be placed in step 2. gained material in amine solvent by the ratio of material with carbon element raw material and amine solvent, at 60 DEG C, processes 20～25h, washing, i.e.
?.
7. the modified carbonaceous components prepared by the method described in any one of claim 1～6.
8. the preparation method of a reinforced epoxy material, it is characterised in that: being scattered in by claim 7 gained modified carbonaceous components in acetone and ethanol 1:0 by volume～0.5 solvent formed, wherein the ratio of modified carbonaceous components and solvent is 10～80mg:100mL；Above-mentioned gained mixed solution is mixed with epoxy resin, dispersion, distillation, add curing agent, solidify after mixing, i.e.
?.
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| CN103043650A (en) * | 2012-12-10 | 2013-04-17 | 青岛宝丽曼高分子材料研究院有限公司 | Modified CNT (carbon nano tube) |
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