CN105060268A - Preparation method of CNT (carbon nanotube) microspheres - Google Patents
Preparation method of CNT (carbon nanotube) microspheres Download PDFInfo
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- CN105060268A CN105060268A CN201510400850.5A CN201510400850A CN105060268A CN 105060268 A CN105060268 A CN 105060268A CN 201510400850 A CN201510400850 A CN 201510400850A CN 105060268 A CN105060268 A CN 105060268A
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Abstract
The invention discloses a preparation method of CNT (carbon nanotube) microspheres. Water-insoluble resin is completely dissolved in an organic solvent, then CNTs and a surfactant are added, and a CNT-containing resin mixed solution is obtained through mixing and ultrasonic and even dispersion; the solution is slowly dropped into a container containing a microsphere forming liquid, the CNT-containing resin solution aggregates to form sphere-like bodies for precipitation in an aqueous solution under the surface tension action, CNT-containing microspheres are obtained, taken out and washed repeatedly, and the microspheres with the CNTs and resin polymer molecules penetrating through each other are obtained after drying at the room temperature. The CNT microspheres can be applied to fiber reinforced composite materials, self-healing composite materials, semiconductor device packaging materials and the like, and the dispersity of the CNTs in the composite materials is effectively improved.
Description
Technical field
The invention belongs to matrix material polymer microballoon technical field, be specifically related to a kind of preparation method of carbon nanotube microballoon.
Background technology
Carbon nanotube (CNTs) is a kind of typical one dimensional nano material with very big L/D ratio, has the excellent performance such as mechanics, electricity, calorifics.Carbon nanotubes reinforced polymer based composites becomes study hotspot.But, CNTs is because specific surface area is large and specific surface energy is strong, very easily reunite, resin itself has certain viscosity simultaneously, carbon nanotube is easily made to pile up, be difficult to realize the uniform compound system of carbon nanotube dispersed in enhancing by polymer modification, not only even can not attain the results expected owing to reuniting, make polymer composites proper property decline on the contrary.Therefore, one of key prepared by high-performance carbon nanotube/polymer composites is the dispersion and orientation that will ensure that CNTs is good, could realize interface so to greatest extent and strengthen.
Current, utilizing microballoon in polymer composites, add carbon nanotube is a kind of technology, effectively can reduce carbon nanotube and reunite, improve the boundary strength of carbon nanotube and polymkeric substance.Current most study be from monomer, the carbon nanotube microballoon of polymer overmold is prepared by letex polymerization, suspension polymerization or diffuse-aggregate method, as, CN101850242A discloses a kind of preparation method of styrene-divinylbenzene-carbon nanometer tube copolymerization chromatograph packing material, with styrene-divinylbenzene and carbon nanotube for raw material, dispersion copolymerization method is adopted to prepare monodisperse polystyrene microsphere seed, after seed activation, adopt single step seed swelling method, obtain styrene-divinylbenzene-carbon nanometer tube copolymerization microballoon; [the HyeonseongBak such as Hyeonseong, YoungSooYun, SeYounCho, entl.Incorporationofmultiwalledcarbonnanotubesonthesurfa ceofpolystyrenemicrospheresviaInSitususpensionpolymeriza tion [J] .MacromolecularResearch, 2011,19 (3): 227-232] prepare polystyrene enveloped carbon nanometer tube microballoon by in-situ suspension polymerization from styrene monomer, microballoon shape is spherical in shape.But these methods easily make emulsifying agent or dispersion agent remain in microballoon inside, are difficult to eliminate, thus affect the performance of material.In order to avoid this problem, [the Liu Yunquan such as Liu Yunquan, Chen little Hua, Zhang Ke, etc. reverse microemulsion process synthesizing carbon nanotubes microballoon [J]. Journal of Inorganic Materials, 2009,24 (5): 993-997] etc. when not using emulsifying agent, adopt the carbon nanotube microballoon that the oil phases such as reverse microemulsion process synthesizing cyclohexane 1 alkane, octane are coated, but microballoon shape is irregular, and reaction is comparatively complicated.In view of polyreaction prepares microballoon, the technology utilizing physical method to prepare polymer-based carbon microballoon in recent years also receives publicity gradually, as CN104194007A discloses a kind of polymer-based carbon micro-/ nano filling modifier compound premix preparation method of granules, non-soluble polymer and micro-/ nano filler are dissolved in respectively in two kinds of identical or close water-soluble solvents of performance, phase in version principle is utilized to prepare Preblend particle, regular shape, but size distribution is comparatively large, and this preparation method is also comparatively complicated.CN101440163B discloses a kind of preparation method of polytetrafluorethylenano nano-microsphere, adopts the coated carbon fluoride nano-tube of tetrafluoroethylene, and controls shape and the particle diameter of particle by ultrasonic disperse.Therefore, how to utilize physical method to prepare the microballoon of uniform particle sizes, regular shape, and environmental protection, cost-savingly more and more to come into one's own.
At present, existing a lot of about the report improving polymer composites performance with carbon nanotube both at home and abroad, with Carbon Nanotubes Reinforced Polymer Composites, the performances such as mechanics of composites, calorifics, electricity can be improved, but there is not yet and adopt resinous polymer enveloped carbon nanometer tube to prepare microballoon thus improve the report of carbon nanotube dispersed.
Summary of the invention
Goal of the invention: for solving the technical problem existed in prior art, the present invention proposes a kind of preparation method of carbon nanotube microballoon, effectively improves the dispersiveness of carbon nanotube in polymer composites.
Technique means: for realizing above-mentioned technical purpose, the concrete steps of the preparation method of carbon nanotube microballoon of the present invention are as follows:
(1) mixed resin solution preparation: non-water-soluble resin, tensio-active agent and carbon nanotube are dissolved in organic solvent, 0.01g/ml ~ 0.5g/ml mixed resin solution is obtained through stirring, ultrasonic disperse, wherein, the addition of tensio-active agent is the 0.01wt% ~ 10wt% of non-water-soluble resin quality, and carbon nanotube addition is the 0.01wt% ~ 1.0wt% of non-water-soluble resin quality;
(2) microballoon shaping dope preparation: with resinous material gauge, dispersion agent is dissolved in deionized water and obtains the microballoon shaping dope of 0.002g/ml ~ 0.05g/ml and stir, wherein, the consumption of dispersion agent is the 2wt% ~ 10wt% of non-water-soluble resin quality;
(3) carbon nanotube microballoon preparation: prepared by ultrasonic for the fluoropolymer resin mixing solutions of step (1) rear instillation step (2) microballoon shaping dope in, after stirring, shaping microballoon is leached, and repeatedly clean 3 ~ 5 times with deionized water, obtain carbon nanotube microballoon through drying at room temperature.
Particularly, non-water-soluble resin described in step (1) is in solid-state thermosetting resin or thermoplastic resin under room temperature, wherein, described thermosetting polymer is any one or a few the mixture in epoxy resin, resol and bismaleimides, and described thermoplastic resin is any one or a few the mixture in polyimide, polystyrene, polyethersulfone, polycarbonate and polysulfones.
Preferably, organic solvent described in step (1) is water-miscible organic solvent, for the mixture of any one or a few in acetone, methylethylketone, dehydrated alcohol, tetrahydrofuran (THF), DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or ethylene glycol.
Preferably, the tensio-active agent described in step (1) be Triton X-100, polyoxyethylene 20 sorbitan monolaurate, high molecular weight alkyl ammonium salt segmented copolymer or containing basic color affinity groups segmented copolymer in any one or a few mixture.
Carbon nanotube described in step (1) is any one or a few in single wall, double-walled and multi-walled carbon nano-tubes, and described carbon nanotube contains any one or a few functional group in carboxyl, amino, hydroxyl or sulfydryl or acyl group.Described carbon nanotube can by comprising any one preparation in chemical Vapor deposition process, arc discharge method, sun power method, template or laser evaporization method, its type is not also limited, it can be the carbon nanotube of single wall, double-walled or many walls, carbon nanotube can contain carboxyl, amino, hydroxyl or sulfydryl, thus effectively can improve carbon nanotube dispersiveness in the solution, and can polyreaction be participated in, improve the interface bond strength of polymkeric substance and carbon nanotube.
Dispersion agent described in step (2) is any one or a few the mixture in polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, non-ionic polyacrylamide, polymine, polyvinyl ether.
Preferably, in step (2) and step (3), described stirring uses electronic or magnetic agitation, and stirring velocity is 500 ~ 3000rpm, and churning time is 60 ~ 120min.
In step (3), the speed in mixed with polymers solution instillation collection container is 1.0ml/min ~ 10ml/min.
Beneficial effect: compared with prior art, tool of the present invention has the following advantages:
(1) preparation method of the present invention contributes to carbon nanotube in the polymer dispersed, effectively avoids agglomeration;
(2) the present invention utilizes Solution Dispersion method, can improve the effect of impregnation of polymkeric substance and carbon nanotube, effectively improves the interface bond strength of carbon nanotube and polymkeric substance; And solvent is convenient to reclaim, and can reduce costs, be beneficial to environmental protection;
(3) carbon nanotube microspherulite diameter of the present invention is even, controlled, can be applied to the field of compound material of particular requirement further;
(4) carbon nanotube micro-sphere material utilization ratio of the present invention is high, and apparatus and process is simple, easily expands scale production;
(5) carbon nanotube microballoon of the present invention has good preservation performance at normal temperatures, can be used for fibre reinforced composites, Self-repair Composites, semiconductor packages material, and technique is simple, has very large development prospect.
Accompanying drawing explanation
Fig. 1 is principle schematic prepared by carbon nanotube microballoon of the present invention;
Fig. 2 is the SEM figure that the embodiment of the present invention 1 prepares the exterior appearance of epoxy resin enveloped carbon nanometer tube microballoon;
Fig. 3 is the SEM figure that the embodiment of the present invention 1 prepares the inner carbon nanotube distribution of epoxy resin enveloped carbon nanometer tube microballoon, and wherein, figure (b) is the partial enlarged drawing of figure (a).
Fig. 4 is the SEM figure that the embodiment of the present invention 1 prepares the exterior appearance of polystyrene enveloped carbon nanometer tube microballoon.
Embodiment
Below by way of specific embodiment, foregoing of the present invention is described in further detail.But this should be interpreted as content of the present invention is only limitted to following example.
Inventive principle of the present invention as shown in Figure 1, the present invention utilizes solution to have excellent dispersiveness and the feature of uniform and stable property, first adopt solvent method to be dissolved in organic solvent by non-water-soluble resin, then even carbon nanotube is scattered in resin solution, improve the dispersiveness of carbon nanotube.By phase transition method, make water-fast resin oily liquid under high shear force stirs, be dispersed into microlayer model, and the dispersion agent added, then reduce the interfacial tension of liquid-between liquid and solid-liquid, contribute to the solid particulate after pulverizing liquid liquid phase separation and stop broken particle aggregation and keep dispersion stable, the emulsion that final formation is stable, be i.e. the carbon nanotube microballoon of size distribution 10 ~ 500 μm.Finally by anhydrating and drying, obtain carbon nanotube microballoon.The present invention is described in detail below by specific embodiment.
Embodiment 1
A preparation method for carbon nanotube microballoon, its concrete steps are as follows:
(1) epoxy resin mixing solutions preparation: be dissolved in acetone solvent by solid glycidyl ethers based epoxy resin, stirs and makes it be uniformly dissolved, obtain the epoxy resin solution of 0.01g/ml; With the weighing scale of epoxy resin, by the carboxylic carbon nano-tube of 0.01wt%, Triton X-100 (tritonX-100) tensio-active agent of 0.01wt% adds in epoxy resin solution, stirs 1min, ultrasonic disperse 30min, obtains epoxy resin mixing solutions;
(2) microballoon shaping dope preparation: in epoxy resin quality, 2wt% polyvinylpyrrolidone is dissolved in deionized water, obtains the microballoon shaping dope of 0.002g/ml, and enable electronic or magnetic stirring apparatus and make it stir, stirring velocity is 700rpm;
(3) carbon nanotube microballoon preparation: by the microballoon shaping dope of ultrasonic for the epoxy resin mixing solutions of step (1) rear instillation step (2), drip fast 10ml/min, be after 700rpm stirs 60min, shaping microballoon is leached with stirring velocity, and repeatedly clean 3 ~ 5 times with deionized water, obtain carbon nanotube microballoon through drying at room temperature.To embodiment 1 prepare carbon nanotube microballoon carry out SEM sign, result as shown in Figure 2, as can be seen from the figure, carbon nanotubes microballoon regular shape, surface irregularity.Further SEM sign is carried out to the distribution of carbon nanotube microballoon inner carbon nanotube, result as shown in Figure 3, wherein, figure (b) is the partial enlarged drawing of figure (a), from Fig. 3 (a), carbon nanotube is evenly distributed in epoxy microballoon inside, clearly can see the coated one deck epoxy resin of carbon nano tube surface by Fig. 3 (b).
Embodiment 2
A preparation method for carbon nanotube microballoon, its place different from embodiment 1 is that in step (1), resin solution is 0.5g/ml; The amount of carbon nanotube is 1wt% (weighing scale with resin), and tensio-active agent is 10wt% (weighing scale with resin), stirs 2min, ultrasonic disperse 60min; 10wt% (weighing scale with resin) polyvinylpyrrolidone dispersion agent in step (2), microballoon shaping dope concentration is 0.002g/ml, and stirring velocity is 3000rpm; Drip fast 1.0ml/min in step (3), stirring velocity is that 3000rpm continues to stir 120min after solution all drips off.
Embodiment 3
(1) resol mixing solutions preparation: be dissolved in by solid phenolic resin in acetone solvent, stirs and makes it be uniformly dissolved, obtain the phenol resin solution of 0.01g/ml; With the weighing scale of resol, by the carboxylic carbon nano-tube of 0.05wt%, the polyoxyethylene 20 sorbitan monolaurate of 1.0wt% adds in phenol resin solution, stirs 1min, ultrasonic disperse 45min, obtains resol mixing solutions;
(2) microballoon shaping dope preparation: in resol quality, 2.0wt% polyvinylpyrrolidone is dissolved in deionized water, obtains the microballoon shaping dope of 0.002g/ml, and enable electronic or magnetic stirring apparatus and make it stir, stirring velocity is 900rpm;
(3) carbon nanotube microballoon preparation: by the microballoon shaping dope of ultrasonic for the resol mixing solutions of step (1) rear instillation step (2), drip fast 10ml/min, be after 900rpm stirs 60min, shaping microballoon is leached with stirring velocity, and repeatedly clean 3 ~ 5 times with deionized water, obtain carbon nanotube microballoon through drying at room temperature.
Embodiment 4
(1) bismaleimides mixing solutions preparation: be dissolved in by solid bismaleimides in N-Methyl pyrrolidone solvent, stirs and makes it be uniformly dissolved, obtain the bismaleimide amine aqueous solution of 0.02g/ml; With the weighing scale of bismaleimides, by the carboxylic carbon nano-tube of 0.05wt%, 1.5wt% Triton X-100 adds in bismaleimide amine aqueous solution, stirs 1min, ultrasonic disperse 60min, obtains bismaleimides mixing solutions;
(2) microballoon shaping dope preparation: in bismaleimides quality, 2.0wt% polyvinylpyrrolidone is dissolved in deionized water, obtain the microballoon shaping dope of 0.006g/ml, and enable electronic or magnetic stirring apparatus and make it stir, stirring velocity is 1500rpm;
(3) carbon nanotube microballoon preparation: by the microballoon shaping dope of ultrasonic for the bismaleimides mixing solutions of step (1) rear instillation step (2), drip fast 10ml/min, be after 1500rpm stirs 60min, shaping microballoon is leached with stirring velocity, and repeatedly clean 3 ~ 5 times with deionized water, obtain carbon nanotube microballoon through drying at room temperature.
Embodiment 5
(1) polystyrene mixing solutions preparation: be dissolved in by polystyrene in tetrahydrofuran solvent, stirs and makes it be uniformly dissolved, obtain 0.05g/ml polystyrene solution; With the weighing scale of polystyrene, add the carboxylic carbon nano-tube of 0.01wt%, Triton X-100 (tritonX-100) tensio-active agent of 0.01wt%, stir 1min, ultrasonic disperse 30min, obtain polystyrene mixing solutions;
(2) microballoon shaping dope preparation: in polystyrene quality, 2wt% polyvinylpyrrolidone is dissolved in deionized water, obtains the microballoon shaping dope of 0.005g/ml, and enable electronic or magnetic stirring apparatus and make it stir, stirring velocity is 800rpm;
(3) carbon nanotube microballoon preparation: by the microballoon shaping dope of ultrasonic for the polystyrene mixing solutions of step (1) rear instillation step (2), drip fast 10ml/min, be after 800rpm stirs 60min, shaping microballoon is leached with stirring velocity, and repeatedly clean 3 ~ 5 times with deionized water, obtain carbon nanotube microballoon through drying at room temperature.To embodiment 4 prepare carbon nanotube microballoon carry out SEM sign, result as shown in Figure 4, as can be seen from the figure, carbon nanotubes microballoon regular shape, surface irregularity.
Embodiment 6
A preparation method for carbon nanotube microballoon, its place different from embodiment 4 is that in step (1), solid polymer is polyethersulfone, and water-miscible organic solvent is N,N-dimethylacetamide, and polymers soln is 0.2g/ml; Carbon nanotube is 0.1wt% (weighing scale with polyethersulfone) aminated carbon nano tube, and tensio-active agent is 2.0wt% (weighing scale with polyethersulfone) high molecular weight alkyl ammonium salt block copolymer B YK-9076; Dispersion agent in step (2) is 6.0wt% (weighing scale with polyethersulfone) polyvinylpyrrolidone and polyoxyethylene glycol mixture, microballoon shaping dope concentration 0.01g/ml, and stirring velocity is 1500rmp; Be after 1500rpm stirs 80min, shaping microballoon is leached with stirring velocity in step (3).
Embodiment 7
A preparation method for carbon nanotube microballoon, its place different from embodiment 1 is that in step (1), solid polymer is polysulfones, and water-miscible organic solvent is N-Methyl pyrrolidone, and polymers soln is 0.2g/ml; Carbon nanotube is 0.5wt% (weighing scale with polysulfones) aminated carbon nano tube, tensio-active agent is the block copolymer B YK-2150 of 6wt% (weighing scale with polysulfones) containing basic color affinity groups, in step (2), dispersion agent is 6wt% (weighing scale with polysulfones) polyoxyethylene glycol, microballoon shaping dope concentration 0.01g/ml, stirring velocity is 2000rmp; Be after 2000rpm stirs 80min, shaping microballoon is leached with stirring velocity in step (3).
Embodiment 8
A preparation method for carbon nanotube microballoon, its place different from embodiment 1 is that in step (1), solid polymer is polycarbonate, and water-miscible organic solvent is acetone, and polymers soln is 0.2g/ml; Carbon nanotube is 0.5wt% (weighing scale with polycarbonate) aminated carbon nano tube, tensio-active agent is the block copolymer B YK-2150 of 6wt% (weighing scale with polycarbonate) containing basic color affinity groups, in step (2), dispersion agent is 6wt% (weighing scale with polycarbonate) polyoxyethylene glycol, microballoon shaping dope concentration 0.01g/ml, stirring velocity is 2000rmp; Be after 2000rpm stirs 80min, shaping microballoon is leached with stirring velocity in step (3).
Claims (8)
1. a preparation method for carbon nanotube microballoon, is characterized in that, comprises the steps:
(1) mixed resin solution preparation: non-water-soluble resin, tensio-active agent and carbon nanotube are dissolved in organic solvent, 0.01g/ml ~ 0.5g/ml mixed resin solution is obtained through stirring, ultrasonic disperse, wherein, the addition of tensio-active agent is the 0.01wt% ~ 10wt% of non-water-soluble resin quality, and carbon nanotube addition is the 0.01wt% ~ 1.0wt% of non-water-soluble resin quality;
(2) microballoon shaping dope preparation: with resinous material gauge, dispersion agent is dissolved in deionized water and obtains the microballoon shaping dope of 0.002g/ml ~ 0.05g/ml and stir, wherein, the consumption of dispersion agent is the 2wt% ~ 10wt% of non-water-soluble resin quality;
(3) carbon nanotube microballoon preparation: prepared by ultrasonic for the mixed resin solution of step (1) rear instillation step (2) microballoon shaping dope in, after stirring, shaping microballoon is leached, and repeatedly clean 3 ~ 5 times with deionized water, obtain carbon nanotube microballoon through drying at room temperature.
2. the preparation method of carbon nanotube microballoon according to claim 1, it is characterized in that, non-water-soluble resin described in step (1) is in solid-state thermosetting resin or thermoplastic resin under room temperature, wherein, described thermosetting resin is any one or a few the mixture in epoxy resin, resol and bismaleimides, and described thermoplastic resin is any one or a few the mixture in polyimide, polystyrene, polyethersulfone, polycarbonate and polysulfones.
3. the preparation method of carbon nanotube microballoon according to claim 1, it is characterized in that, organic solvent described in step (1) is water-miscible organic solvent, for acetone, methylethylketone, dehydrated alcohol, tetrahydrofuran (THF), N, any one or a few mixture in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or ethylene glycol.
4. the preparation method of carbon nanotube microballoon according to claim 1, it is characterized in that, the tensio-active agent described in step (1) be Triton X-100, polyoxyethylene 20 sorbitan monolaurate, high molecular weight alkyl ammonium salt segmented copolymer or containing basic color affinity groups segmented copolymer in any one or a few mixture.
5. the preparation method of carbon nanotube microballoon according to claim 1; it is characterized in that; carbon nanotube described in step (1) is any one or a few in single wall, double-walled and multi-walled carbon nano-tubes, and described carbon nanotube contains any one or a few functional group in carboxyl, amino, hydroxyl or sulfydryl or acyl group.
6. according to the preparation method of the carbon nanotube microballoon described in claim 1, it is characterized in that, the dispersion agent described in step (2) is any one or a few the mixture in polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, non-ionic polyacrylamide, polymine, polyvinyl ether.
7. according to the preparation method of the carbon nanotube microballoon described in claim 1, it is characterized in that, in step (2) and step (3), described stirring uses electronic or magnetic agitation, stirring velocity is 500 ~ 3000rpm, and churning time is 60 ~ 120min.
8. according to the preparation method of the carbon nanotube microballoon described in claim 1, it is characterized in that, in step (3), the speed in mixed resin solution instillation microballoon shaping dope is 1.0ml/min ~ 10ml/min.
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| CN112909250A (en) * | 2019-11-19 | 2021-06-04 | 中能中科（天津）新能源科技有限公司 | Carbon material microsphere, lithium carbon powder, and preparation method and application thereof |
| CN112909250B (en) * | 2019-11-19 | 2022-04-26 | 中能中科（天津）新能源科技有限公司 | Carbon material microsphere, lithium carbon powder, and preparation method and application thereof |
| CN112479182A (en) * | 2020-11-27 | 2021-03-12 | 中宝(西安)科技集团有限公司 | Preparation method of carbon nanotube hollow sphere composite material and composite material |
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