CN101955631A - Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material - Google Patents
Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a polyaniline modified multi-wall carbon canotubes/epoxy resin composite material. The preparation method comprises the following steps of: firstly, modifying the surfaces of multi-wall carbon canotubes with conducting macromolecular polyaniline through the doping of a functional protonic acid and the in situ polymerization of aniline; then, dispersing the multi-wall carbon canotubes with surfaces modified by polyaniline to an epoxy resin macromolecular solution, and adding a curing agent after removing the solvent; and finally, carrying out vacuum degassing, pouring into molds, heating and curing to prepare the composite material. The preparation method has simple process, low production cost and obvious reinforcing and toughening effects, and can effectively prevent the aggregation of the multi-wall carbon canotubes in epoxy resin and increase the dispersibility and the interfacial bonding of the multi-wall carbon canotubes in the epoxy resin. In addition, the conducting polyaniline is coated on the surfaces of the multi-wall carbon canotubes, and thus, the polyaniline modified multi-wall carbon canotubes/epoxy resin composite material acquires good mechanical properties and good antistatic function.
Description
Technical field
The invention belongs to the nano composite material technical field, be specifically related to a kind of preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material.
Background technology
Because characteristics such as Resins, epoxy has that cohesiveness is strong, corrosion-resistant, good insulation preformance and intensity height, therefore fields such as coating, tackiness agent, Electronic Packaging and matrices of composite material have been widely used at present, but its shortcoming is that internal stress is big after solidifying, therefore peel off easily and ftracture, and antifatigue, heat-resisting and poor impact toughness, the result causes range of application to be restricted.Carbon nanotube is a kind of hollow carbon cage pipe that is formed by the cylindric graphite flake of single or multiple lift, diameter is in nanometer scale, length is in micron dimension, and its intensity and toughness are better than other fiber, and has special conduction, heat conduction, magnetic, corrosion-resistant and lightweight.Compare with Single Walled Carbon Nanotube, the production cost of multi-walled carbon nano-tubes is low, and caliber can select in the scope of broad, therefore based on the matrix material of multi-walled carbon nano-tubes closing to reality and can satisfy industrialized requirement easily more.
Multi-walled carbon nano-tubes and Resins, epoxy is compound, if can give full play to the characteristics such as minor diameter, big L/D ratio, strong mechanical performance and special electromagnetic performance of multi-walled carbon nano-tubes, then be expected to obtain the structure or the functional composite material of excellent combination property.Therefore, present multi-walled carbon nano-tubes/epoxy resin composite material has been subjected to the extensive concern of Chinese scholars.Yet, assemble because multi-walled carbon nano-tubes easily mutually twines, therefore be difficult to disperse, and since its surface inactive former thus with the bad adhesion of resin, these all can hinder the development and the application of multi-walled carbon nano-tubes/epoxy resin composite material.Studies show that how making multi-walled carbon nano-tubes obtain homodisperse in Resins, epoxy and reaching the good interface bonding is the key that obtains desirable matrix material.
At present, both at home and abroad mainly by adding the tensio-active agent hydrotropy, the multi-wall carbon nano-tube tube-surface is handled and the multi-wall carbon nano-tube tube-surface being carried out means such as chemical modification and improve and improve dispersiveness and the interface performance of multi-walled carbon nano-tubes in Resins, epoxy with coupling agent.Yet, owing to be modified at a little less than the repulsive interaction of the undersized functional group of multi-wall carbon nano-tube tube-surface, tensio-active agent or coupling agent molecule generation, simultaneously, because the viscosity of Resins, epoxy and macromole solution thereof is higher, therefore the homodisperse problem of multi-walled carbon nano-tubes in the high viscosity resins system after surface treatment or the modification still can not obtain fine solution, will cause the microcosmic of matrix material to form heterogeneity like this, the various performances that hindered multi-walled carbon nano-tubes thus are not fully exerted in matrix material.
Polyaniline is a kind of conducting polymer that receives much concern, have that raw materials cost is low, environmental stability good, be easy to dissolving processing, therefore the advantage of protection against corrosion and reversible electro-chemical properties obtains widespread use in fields such as battery, anticorrosion, antistatic, absorption of electromagnetic wave.Can obtain nuclear-shell nano composite structure that multi-walled carbon nano-tubes is evenly coated by polyaniline by in-situ polymerization, this is an effective way [Appl.Phys.A Vol.80,1813 (2005)] that solves multi-walled carbon nano-tubes bad dispersibility in polymkeric substance.Because synergistic effect, this coaxial cladded type nuclear-shell nano composite structure can combine the workability of mechanical property, electromagnetic performance, thermostability and the polyaniline of multi-walled carbon nano-tubes, so can be applicable in the advanced composite material.In addition, when with this nuclear-when the shell nano composite structure is dispersed in the solvent, the polyaniline coating layer will be in solvent swelling, then separated between multi-walled carbon nano-tubes by the polyaniline macromole, therefore assemble and be difficult to take place [J.Mater.Sci.Mater.El.Vol.20 (6), 517 (2009), Mat.Sci.Eng.B-Solid 151 (3), and 210 (2008)].Yet, up to the present do not find as yet to use the polyaniline modifying multiwall carbon nano-tube, then prepare multi-walled carbon nano-tubes/epoxy resin composite material and obtain the good content that strengthens toughening effect and be seen in report.
Summary of the invention
In order to address the above problem, the object of the present invention is to provide a kind ofly to strengthen toughening effect obviously and can effectively improve the dispersiveness of multi-walled carbon nano-tubes in Resins, epoxy and the preparation method of the polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material of interface agglutinating.
In order to achieve the above object, the preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material provided by the invention comprises the following step that carries out in order:
(1) multi-walled carbon nano-tubes with dry surface band carboxyl joins in the function protonic acid solution, ultrasonic agitation 0.5～1 hour, then aniline is added drop-wise in the above-mentioned multiple-wall carbon nanotube suspension, the dropping time is 1 hour, ultrasonic agitation is 1 hour afterwards, ammonium persulfate aqueous solution is added drop-wise in the above-mentioned reaction system again, the dropping time is 0.5 hour, continue reaction extremely reaction end in 2～4 hours after dripping, above-mentioned whole polymerization process carries out under 35 ℃ temperature and ultrasonic agitation all the time, then through acetone breakdown of emulsion, deionized water wash, obtain polyaniline-modified multi-walled carbon nano-tubes after filtering with microporous membrane and the drying;
(2) above-mentioned polyaniline-modified multi-walled carbon nano-tubes is joined in the solvent, ultrasonic agitation 1 hour adds Resins, epoxy then, continues ultrasonic agitation 1 hour, heats afterwards to vapor away solvent; The adding solidifying agent also stirred 0.5 hour; With the vacuum outgas 1 hour under 50 ℃ temperature of above mixed system, be poured in the mould at last, and under 80～120 ℃ temperature, heat 2～4 hours until curing molding, can obtain polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material.
Described function protonic acid is selected from a kind of of Witco 1298 Soft Acid, sodium laurylsulfonate+hydrochloric acid, camphorsulfonic acid, naphthene sulfonic acid and p-methyl benzenesulfonic acid.
Described Resins, epoxy is E-51 or E-44.
Described solvent is selected from a kind of in acetone, tetrahydrofuran (THF), toluene and the trichloromethane.
Described solidifying agent is a 2-ethyl-4-methylimidazole.
In described step (1), the multi-walled carbon nano-tubes of surface band carboxyl and the amount ratio of aniline are 1g: 5g; The amount ratio of aniline and ammonium persulphate is 1mol: 1mol; The amount ratio of aniline and function protonic acid is 1mol: 0.8～1mol.
In described step (2), the amount ratio of polyaniline-modified multi-walled carbon nano-tubes and Resins, epoxy is 1～10g: 100g; The amount ratio of solidifying agent and Resins, epoxy is 6～8g: 100g.
The preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material provided by the invention is the surface that at first by the in-situ polymerization of function protonic acid doping and aniline conductive polymer polyanilinc is modified at multi-walled carbon nano-tubes, multi-walled carbon nano-tubes after the polyaniline finishing is dispersed in the Resins, epoxy macromole solution then, remove the back of desolvating and add solidifying agent, after vacuum outgas, be poured into and be heating and curing in the mould and make matrix material.Wherein can realize utilizing the surface modification of conducting polymer to multi-walled carbon nano-tubes by aniline at the in-situ polymerization of multi-wall carbon nano-tube tube-surface, compare with small size functional group or small molecules, the polyaniline macromolecular chain can produce stronger repulsion and sterically hindered.After being dispersed in polyaniline-modified multi-walled carbon nano-tubes in the epoxy resin solution, swelling will take place in the polyaniline coating layer, to destroy the avidity between multi-walled carbon nano-tubes, therefore make it be difficult to assemble in Resins, epoxy, thereby will obtain homodisperse.In addition, be to be connected with π-π * conjugated link(age) between multi-walled carbon nano-tubes and polyaniline by hydrogen bond, the amino end group of polyaniline combines by chemical bond with the epoxy group(ing) of Resins, epoxy, can make matrix material obtain stronger interface interaction like this.In addition, doped polyaniline has light weight, conduction, absorption hertzian wave and Anticorrosive Character, it can bring into play the synergistic effect of nucleocapsid structure after being modified at the multi-wall carbon nano-tube tube-surface, thereby makes matrix material obtain good mechanical property and have good antistatic and absorption of electromagnetic wave performance concurrently.Compare with Resins, epoxy, the polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material mechanical property after the curing significantly improves, and surface resistivity is 10
3～10
6Ω/.In addition, this preparation method has also that technology is simple, production cost is low, and is easy to realize advantage such as industrialization, therefore can be widely used in aviation, electronic apparatus, electromechanical equipment, automobile, shipbuilding, military project and field of wind power generation.
Embodiment
Preparation method to polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material provided by the invention is elaborated below in conjunction with specific embodiment.
Embodiment 1:
(1) multi-walled carbon nano-tubes with 0.2g dry surface band carboxyl joins in 200ml (0.04mol/l) dodecylbenzenesulfonic acid solution ultrasonic agitation 0.5 hour; Then with 1
g(0.01mol) aniline is added dropwise in the above-mentioned multiple-wall carbon nanotube suspension, and the dropping time is 1 hour, and ultrasonic agitation is 1 hour afterwards; Again 50ml (0.2mol/l) ammonium persulfate aqueous solution is added drop-wise in the above-mentioned reaction system, the dropping time is 0.5 hour, continue reaction extremely reaction end in 2 hours afterwards, above-mentioned whole polymerization process carries out under 35 ℃ temperature and ultrasonic agitation all the time, through the acetone breakdown of emulsion, obtain polyaniline-modified multi-walled carbon nano-tubes after deionized water wash, filtering with microporous membrane and the drying then;
(2) the above-mentioned polyaniline-modified multi-walled carbon nano-tubes of 1g is joined in the 50ml acetone, ultrasonic agitation 1 hour adds the 100g epoxy resin E-44 then, and ultrasonic agitation 1 hour heats under 70 ℃ temperature afterwards to vapor away acetone; Adding 6g 2-ethyl-4-methylimidazole also stirred 0.5 hour; With the vacuum outgas 1 hour under 50 ℃ temperature of above-mentioned mixed system, be poured at last in the mould, heating 2 hours under 80 ℃ temperature earlier then was warming up to 120 ℃ of reheat 2 hours, until curing molding.Matrix material behind the above-mentioned curing molding is taken out, and the room temperature cooling can obtain polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material.
Comparative example
In the 100g epoxy resin E-44, add the 6g 2-ethyl-4-methylimidazole, under 40～50 ℃ temperature, stirred 0.5 hour.With the vacuum outgas 1 hour under 50 ℃ temperature of above-mentioned mixed system, be poured into then in the mould, heating 2 hours under 80 ℃ temperature earlier then was warming up to 120 ℃ of reheat 2 hours, until curing molding.Matrix material behind the above-mentioned curing molding is taken out, and room temperature is cooled off, and is not added the product (being called for short pure EP) of polyaniline modification multi-walled carbon nano-tubes.
Embodiment 2:
(1) multi-walled carbon nano-tubes with 0.2g dry surface band carboxyl joins in 200ml (0.05mol/l) the camphorsulfonic acid solution ultrasonic agitation 0.5 hour; Then 1g (0.01mol) aniline is added dropwise in the above-mentioned multiple-wall carbon nanotube suspension, the dropping time is 1 hour, and ultrasonic agitation is 1 hour afterwards; Again 50ml (0.2mol/l) ammonium persulfate aqueous solution is added drop-wise in the above-mentioned reaction system, the dropping time is 0.5 hour, continue reaction extremely reaction end in 3 hours afterwards, above-mentioned whole polymerization process carries out under 35 ℃ temperature and ultrasonic agitation all the time, through the acetone breakdown of emulsion, obtain polyaniline-modified multi-walled carbon nano-tubes after deionized water wash, filtering with microporous membrane and the drying then;
(2) the above-mentioned polyaniline-modified multi-walled carbon nano-tubes of 5g is joined in the 50ml acetone, ultrasonic agitation 1 hour adds 100g Resins, epoxy E-51 then, and ultrasonic agitation 1 hour heats under 70 ℃ temperature afterwards to vapor away acetone; Adding 8g 2-ethyl-4-methylimidazole also stirred 0.5 hour; With the vacuum outgas 1 hour under 50 ℃ temperature of above-mentioned mixed system, be poured at last in the mould, heating 2 hours under 80 ℃ temperature earlier then was warming up to 120 ℃ of reheat 2 hours, until curing molding.Matrix material behind the above-mentioned curing molding is taken out, and the room temperature cooling can obtain polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material.
Embodiment 3:
(1) multi-walled carbon nano-tubes with 0.2g dry surface band carboxyl joins in 200ml (0.05mol/l) the p-methyl benzenesulfonic acid solution ultrasonic agitation 0.5 hour; Then 1g (0.01mol) aniline is added dropwise in the above-mentioned multiple-wall carbon nanotube suspension, the dropping time is 1 hour, and ultrasonic agitation is 1 hour afterwards; Again 50ml (0.2mol/l) ammonium persulfate aqueous solution is added drop-wise in the above-mentioned reaction system, the dropping time is 0.5 hour, continue reaction extremely reaction end in 4 hours afterwards, above-mentioned whole polymerization process carries out under 35 ℃ temperature and ultrasonic agitation all the time, then through filtering with microporous membrane, deionized water wash and dry after and obtain polyaniline-modified multi-walled carbon nano-tubes;
(2) the above-mentioned polyaniline-modified multi-walled carbon nano-tubes of 10g is joined in the 50ml tetrahydrofuran (THF), ultrasonic agitation 1 hour adds the 100g epoxy resin E-44 then, and ultrasonic agitation 1 hour heats under 70 ℃ temperature afterwards to vapor away tetrahydrofuran (THF); Adding 6g 2-ethyl-4-methylimidazole also stirred 0.5 hour; With the vacuum outgas 1 hour under 50 ℃ temperature of above-mentioned mixed system, be poured at last in the mould, heating 2 hours under 80 ℃ temperature earlier then was warming up to 120 ℃ of reheat 2 hours, until curing molding.Matrix material behind the above-mentioned curing molding is taken out, and the room temperature cooling can obtain polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material.
Now the pure EP that obtains in the polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material that obtains among above-mentioned all embodiment and the comparative example is carried out Mechanics Performance Testing according to following testing method, test result sees Table 1.
Mechanic property test method:
Tensile property test:, adopt Testometric M350-20kN universal testing machine to measure tensile strength, modulus in tension, elongation at break, rate of extension 2mm/min according to GB/T 2567-2008 standard.
Bending property test:, adopt the U.S. M350-20kN of Testometric company universal testing machine to measure flexural strength, bending elastic modulus, loading rate 2mm/min according to GB/T 2567-2008 standard.
Impact property test:, adopt the Chengde XCJ-50 of trier factory impact tester to measure unnotched impact strength according to GB/T 2567-2008 standard.
Surface resistivity test:, adopt the SDY-5 of Guangzhou Semiconductor Material Inst. type four electrode conductance rate instrument to measure surface resistivity by four electrode method according to GB/T 15662 standards.
Material properties test result in table 1, the embodiment of the invention and the comparative example
From the content of table 1 as can be seen, utilize the mechanical property of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material that method provided by the invention prepares obviously to improve than pure EP.Simultaneously, the surface resistivity of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material is 10
3～10
6Therefore Ω/ can satisfy the service requirements of antistatic material.
Claims (7)
1. the preparation method of a polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material, it is characterized in that: described preparation method comprises the following step that carries out in order:
(1) multi-walled carbon nano-tubes with dry surface band carboxyl joins in the function protonic acid solution, ultrasonic agitation 0.5～1 hour, then aniline is added drop-wise in the above-mentioned multiple-wall carbon nanotube suspension, the dropping time is 1 hour, ultrasonic agitation is 1 hour afterwards, ammonium persulfate aqueous solution is added drop-wise in the above-mentioned reaction system again, the dropping time is 0.5 hour, continue reaction extremely reaction end in 2～4 hours after dripping, above-mentioned whole polymerization process carries out under 35 ℃ temperature and ultrasonic agitation all the time, then through the acetone breakdown of emulsion, deionized water wash, obtain polyaniline-modified multi-walled carbon nano-tubes after filtering with microporous membrane and the drying;
(2) above-mentioned polyaniline-modified multi-walled carbon nano-tubes is joined in the solvent, ultrasonic agitation 1 hour adds Resins, epoxy then, continues ultrasonic agitation 1 hour, heats afterwards to vapor away solvent; The adding solidifying agent also stirred 0.5 hour; With the vacuum outgas 1 hour under 50 ℃ temperature of above mixed system, be poured in the mould at last, and under 80～120 ℃ temperature, heat 2～4 hours until curing molding, can obtain polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material.
2. the preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material according to claim 1, it is characterized in that: described function protonic acid is selected from a kind of of Witco 1298 Soft Acid, sodium laurylsulfonate+hydrochloric acid, camphorsulfonic acid, naphthene sulfonic acid and p-methyl benzenesulfonic acid.
3. the preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material according to claim 1, it is characterized in that: described Resins, epoxy is E-51 or E-44.
4. the preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material according to claim 1 is characterized in that: described solvent is selected from a kind of in acetone, tetrahydrofuran (THF), toluene and the trichloromethane.
5. the preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material according to claim 1, it is characterized in that: described solidifying agent is a 2-ethyl-4-methylimidazole.
6. the preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material according to claim 1 is characterized in that: in described step (1), the multi-walled carbon nano-tubes of surface band carboxyl and the amount ratio of aniline are 1g: 5g; The amount ratio of aniline and ammonium persulphate is 1mol: 1mol; The amount ratio of aniline and function protonic acid is 1mol: 0.8～1mol.
7. the preparation method of polyaniline-modified multi-walled carbon nano-tubes/epoxy resin composite material according to claim 1, it is characterized in that: in described step (2), the amount ratio of polyaniline-modified multi-walled carbon nano-tubes and Resins, epoxy is 1～10g: 100g; The amount ratio of solidifying agent and Resins, epoxy is 6～8g: 100g.
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