CN102875843A - Modified carbon nanotube and preparation method thereof - Google Patents
Modified carbon nanotube and preparation method thereof Download PDFInfo
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- CN102875843A CN102875843A CN2012103904615A CN201210390461A CN102875843A CN 102875843 A CN102875843 A CN 102875843A CN 2012103904615 A CN2012103904615 A CN 2012103904615A CN 201210390461 A CN201210390461 A CN 201210390461A CN 102875843 A CN102875843 A CN 102875843A
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Abstract
The invention relates to a modified carbon nanotube and a preparation method thereof. The preparation method comprises the following steps: dissolving polyaniline in dimethylsulfoxide, dropwisely adding hyperbranched polysiloxane containing epoxy group, and adding hydrochloric acid to obtain hyperbranched-polysiloxane modified polyaniline; and adding the hyperbranched-polysiloxane modified polyaniline and carbon nanotube into dimethylsulfoxide, precipitating in methanol, carrying out vacuum filtration, and washing to obtain the modified carbon nanotube. The hyperbranched-polysiloxane modified polyaniline conductive layer is coated on the surface of the carbon nanotube, and the content of the coating layer can be regulated to control the conductivity of the modified carbon nanotube, thereby providing possibility for preparing conductive and dielectric materials with functions of high dielectric constant, low dielectric loss and the like as well as regulating and controlling properties. The hyperbranched polysiloxane contains epoxy, hydroxy and other active groups, and thus, lays favorable foundation for research and development of modified carbon nanotube-resin composite and novel functional materials. The modified carbon nanotube provided by the invention has the characteristics of wide preparation method applicability and simple operating technique.
Description
Technical field
The present invention relates to a kind of modified carbon nano-tube and preparation method thereof.
Background technology
Carbon nanotube has larger length-to-diameter ratio, it is a kind of One-dimensional Quantum material with special construction, light weight, hexagonal structure is perfect, have high-modulus, high strength, and the ideal that is considered to multifunctional material strengthens body, and its application in various fields has caused various countries scientists' common concern.Wherein, a compound important application form that becomes carbon nanotube of carbon nanotube and polymkeric substance.Closely decades, Chinese scholars was launched large quantity research, and the result shows that the dispersiveness of carbon nanotube is to affect the key factor that can its excellent properties be given full play to.Yet the characteristic that carbon nanotube is very easily reunited has determined that carbon nanotube is difficult to obtain good dispersiveness in polymkeric substance, so the modification of carbon nanotube becomes the important content of carbon nanotube and associated materials research and development thereof.
At present, a method of effectively improving carbon nanotube dispersed is to form coating layer outside carbon nanotube.Document (Mei Yang, Yong Gao, Huaming Li, Alex Adronov.Functionalization of multiwalled carbon nanotubes with polyamide 6by anionic ring-opening polymerization.Carbon; 45; 2007; 2327 – 2333.) reported that in the carbon nano tube surface of isocyano by anionic ring-opening polymerization grafting nylon 6, the carbon nanotube after the modification can be dispersed in the organic solvent uniformly.But the method is based upon carbon nanotube is carried out significantly having destroyed the surface of carbon nanotube on the chemically treated basis of multistep, therefore, be unfavorable for keeping the original performance advantage of carbon nanotube.
The people such as Mai are carrying out carbon nanotube on the chemically treated basis of multistep high temperature under long-time equally, the super branched polyurethane of the terminal hydroxyl of chemical graft on carbon nanotube is (referring to document: Yingkui Yang, Xiaolin Xie, Jingao Wu, Zhifang Yang, Xiaotao Wang, Yiu-Wing Mai.Multiwalled Carbon Nanotubes Functionalized by Hyperbranched Poly (urea-urethane) s by aOne-Pot Polycondensation.Macromol.Rapid Commun; 2006; 27; 1695 – 1701.).Resulting modified carbon nano-tube can have good dispersiveness in polar solvent, but heat decomposition temperature is lower than original carbon nanotube.
Can be seen by above-mentioned prior art, although present modified carbon nano-tube technology of preparing has reached the purpose of certain aspect modification, significantly damage inevitably the perfect graphite-structure of carbon pipe, cause its excellent properties to reduce.Therefore, modified carbon nano-tube of development of new and preparation method thereof is of great significance and value.
Summary of the invention
The deficiency that exists in order to overcome prior art, the object of the present invention is to provide under a kind of prerequisite keeping the carbon nanotube high conductivity, reach simultaneously and prevent that carbon nanotube from reuniting and give the modified carbon nano-tube of the reactive dual function of modified carbon nano-tube, and its preparation method has simple, as to be suitable for large-scale application characteristics.
Realize that the technical scheme of the object of the invention provides a kind of preparation method of modified carbon nano-tube, comprises the steps:
1, at N
2Protection is lower, in mass ratio, 10 parts of polyanilines is dissolved in 500～1000 parts of dimethyl sulfoxide (DMSO), obtains polyaniline solutions; In polyaniline solutions, dropwise add 1～3 part and contain the hyperbranched polyorganosiloxane of epoxy group(ing) and 0.05～0.1 part hydrochloric acid, under 20～50 ℃ temperature condition, stirred 5～72 hours; After reaction finished, washing, suction filtration were removed solvent, obtain the hyperbranched polyorganosiloxane modified polyaniline;
2, in mass ratio, the hyperbranched polyorganosiloxane modified polyaniline of 0.5 part carbon nanotube and 0.025～5 part is joined in 15～25 parts of dimethyl sulfoxide (DMSO), stir and supersound process 20～40min obtains reaction product; To precipitate in 40～50 parts of methyl alcohol of reaction product adding, suction filtration and washing obtain modified carbon nano-tube.
In technical solution of the present invention, described carbon nanotube is single wall or multi-walled carbon nano-tubes, or its combination.Described polyaniline is the polymkeric substance of phenyl amines monomer, can be aniline, Ortho Toluidine, m-sulfanilic acid, 2, the homopolymer of 3-xylidine, meta-aminotoluene, ORTHO AMINO PHENOL SULPHONIC, anthranilic acid, gavaculine, or the multipolymer of their arbitrary combination.
In technical solution of the present invention, the hyperbranched polyorganosiloxane that contains epoxy group(ing) that adopts is prior art, as being that the Chinese invention patent preparation method of CN102199294A can obtain by publication number, concrete steps are: in molar ratio, 11～16 parts of distilled water and 10 parts of trialkoxy silanes that contain epoxide group are mixed, add 30～60 parts of solvent dehydrated alcohols, under agitation condition, slowly drip again 0.001～0.003 part of catalyzer; Be warming up to 50～60 ℃ after dropwising, react after 4～7 hours, through washing, drying, obtain containing the hyperbranched polyorganosiloxane of epoxy group(ing).Described catalyzer is hydrochloric acid, sulfuric acid, tosic acid, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, sodium hydroxide or potassium hydroxide.The described trialkoxy silane that contains epoxy group(ing) is 3-glycidyl ether oxygen base propyl trimethoxy silicane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, 2-(3,4-epoxy cyclohexane alkyl) ethyl triethoxysilane, or their arbitrary combination.
Technical solution of the present invention also comprises a kind of modified carbon nano-tube that obtains by above-mentioned preparation method.
Compared with prior art, the obtained beneficial effect of the present invention is:
1, the present invention coats the hyperbranched polyorganosiloxane modified polyaniline in carbon nano tube surface, avoid adopting the graphite-structure of chemical treatment destroying carbon nanometer tube, hyperbranched polyorganosiloxane modified polyaniline side chain relies on contained a large amount of phenyl ring, quinone ring structure and carbon nano tube surface to form large π system, be adsorbed on the carbon nanotube by π-π effect, at the carbon nano tube surface coated polymer, thereby destroyed carbon nanotube self agglomerating force, reached the purpose of dispersing Nano carbon tubes.
2, the hyperbranched polyorganosiloxane modified polyaniline that synthesizes of the present invention contains many polyaniline chains, but not single simple linear polymer chain has guaranteed that less add-on just can realize the good distribution to carbon nanotube.
3, the side chain of hyperbranched polyorganosiloxane modified polyaniline is the polyaniline that mixes through acid, it has higher specific conductivity, therefore, guaranteed that carbon nanotube has high specific conductivity, for the functional materialss such as preparation electro-conductive material, high dielectric constant material provide performance guarantee.
4, dissaving structure is given a large amount of epoxy of hyperbranched polyorganosiloxane modified polyaniline, hydroxyl isoreactivity reactive group, for modified carbon nano-tube obtains good dispersiveness and good chemical interface reactive force provides powerful support in polymkeric substance.
5, the outstanding thermotolerance of hyperbranched polyorganosiloxane that the prepared hyperbranched polyorganosiloxane modified polyaniline of the present invention is integrated has the thermotolerance that is better than unmodified polyaniline.
Description of drawings
Fig. 1 is hyperbranched polyorganosiloxane, the polyaniline of the embodiment of the invention 1 preparation, the infrared spectrum of hyperbranched polyorganosiloxane modified polyaniline;
Fig. 2 is the polyaniline of the embodiment of the invention 1 preparation, the ultraviolet-visible light spectrogram of hyperbranched polyorganosiloxane modified polyaniline;
Fig. 3 is polyaniline, the hyperbranched polyorganosiloxane modified polyaniline of the embodiment of the invention 1 preparation
13The C nmr spectrum;
Fig. 4 is the polyaniline of the embodiment of the invention 1 preparation, the scanning electron microscope diagram of hyperbranched polyorganosiloxane modified polyaniline;
Fig. 5 is the polyaniline of the embodiment of the invention 1 preparation, the X-ray diffraction spectrogram of hyperbranched polyorganosiloxane modified polyaniline;
Fig. 6 is the polyaniline of the embodiment of the invention 1 preparation, the specific conductivity graphic representation of hyperbranched polyorganosiloxane modified polyaniline;
Fig. 7 is the polyaniline of the embodiment of the invention 1 preparation, the thermogravimetric curve figure of hyperbranched polyorganosiloxane modified polyaniline;
Fig. 8 is the structural representation of hyperbranched polyorganosiloxane modified polyaniline provided by the invention;
Fig. 9 is the modified carbon nano-tube of the embodiment of the invention 1～4 preparation, the X-ray diffraction spectrogram of carbon nanotube;
Figure 10 is the modified carbon nano-tube of the embodiment of the invention 1～4 preparation, the Raman spectrogram of carbon nanotube;
Figure 11 is the scanning electron microscope diagram of the modified carbon nano-tube of the embodiment of the invention 1～4 preparation;
Figure 12 is modified carbon nano-tube, the AC conductivity histogram of carbon nanotube under the 10Hz frequency that the embodiment of the invention 2 and 4 provides;
Figure 13 is that the specific inductivity of the prepared matrix material of the comparative example 1 that provides of embodiment 4 and comparative example 2 is with the graphic representation of frequency change;
Figure 14 is that the specific inductivity of the prepared matrix material of the comparative example 1 that provides of embodiment 4 and comparative example 2 is with the graphic representation of frequency change.
Embodiment
Below in conjunction with accompanying drawing, embodiment and comparative example, technical solution of the present invention will be further described.
Embodiment 1
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get the 30mL dehydrated alcohol and make solvent, to wherein adding 23.6g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2Protection, slowly dropwise to add 2.0g pH under the magnetic agitation condition be 2 HCl solution; Dropwise, be warming up to 50 ℃ and continue reaction 7 hours; React complete after, carry out underpressure distillation, obtain the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.Weight-average molecular weight is 7500.Its infrared spectrum as shown in Figure 1.
Respectively 0.9g aniline, 1.1g Ortho Toluidine and 1.7g m-sulfanilic acid are mixed, in mixture, add 150mL hydrochloric acid soln (0.2mol/L); At N
2Under protection and 0～5 ℃ of condition, mechanical stirring 30min.Dropwise add subsequently 100mL ammonium persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 5 hours until reaction finishes, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.Limiting viscosity is 0.32dL/g.Its infrared spectrum, ultraviolet-visible light spectrogram,
13C nmr spectrum, scanning electronic microscope, X-ray diffraction spectrum, specific conductivity curve and thermogravimetric curve are respectively shown in accompanying drawing 1,2,3,4,5,6 and 7.
In the 45mL dimethyl sulfoxide (DMSO), add 0.5g polyaniline, N
2Under protection, the 25 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.1g hyperbranched polyorganosiloxane and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 74.17%.Its structural representation is referring to accompanying drawing 8, in the present embodiment,
R
1/R
3=H/SO
3H R
2/R
4=H/CH
3 
The infrared spectrum of the hyperbranched polyorganosiloxane modified polyaniline of present embodiment preparation, ultraviolet-visible light spectrogram,
13C nmr spectrum, scanning electronic microscope, X-ray diffraction spectrum, specific conductivity curve and thermogravimetric curve are respectively shown in accompanying drawing 1,2,3,4,5,6 and 7.
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 0.5g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.Its X-ray diffraction spectrum, Raman spectrogram, scanning electron microscope diagram are respectively shown in Fig. 9,10,11.
Referring to accompanying drawing 1, it is hyperbranched polyorganosiloxane, the polyaniline in the present embodiment, the infrared spectrum of hyperbranched polyorganosiloxane modified polyaniline.Can find out: (1) hyperbranched polyorganosiloxane modified polyaniline has kept the skeleton structure of polyaniline, at 1090～1180cm
-1The place exists more by force than broad absorption band, is the charateristic avsorption band of Si-O-Si, shows that polyaniline successfully is connected to the periphery of hyperbranched polyorganosiloxane.(2) at 814cm
-1There is weak epoxy absorption peak in the place, although show on the polyaniline amino can with hyperbranched polyorganosiloxane in epoxide group reaction, but hyperbranched polyorganosiloxane is spherical three-dimensional arrangement, sterically hindered larger, epoxide group can not complete reaction, be further changing-nature and application, the novel high polymer material of polyaniline research and development, polymer modification and high performance, multiple functionalized providing may.
Referring to accompanying drawing 2, it is the ultraviolet-visible light spectrogram of polyaniline in the present embodiment, hyperbranched polyorganosiloxane modified polyaniline.Compare with polyaniline, strong blue-shifted phenomenon has all appearred in the wavelength of the absorption band that two intensity of hyperbranched polyorganosiloxane modified polyaniline are higher, shows that the conjugated degree of polymkeric substance reduces, and super branched molecule is successfully introduced in the polyaniline.
Referring to accompanying drawing 3, it is polyaniline and hyperbranched polyorganosiloxane modified polyaniline in the present embodiment
13The C nmr spectrum.Compare with the spectrogram of polyaniline curve, occur many new in the spectrogram of hyperbranched polyorganosiloxane modified polyaniline
13The C fignal center shows that hyperbranched polyorganosiloxane is introduced in the polyaniline by the reaction of epoxy group(ing) with amino.
Referring to table 1, it is the ultimate analysis EDS table of the terpolymer aniline that makes of present embodiment and hyperbranched polyorganosiloxane modified polyaniline.Therefrom as can be known, in the aniline copolymer in the monomer of the atomic percentage conc of C, N, S, O and adding each constituent content similar, show that it really is the terpolymer of aniline; Si, O content increase in the hyperbranched polyorganosiloxane modified polyaniline, C, N, S content slightly reduce, show by the amino on the polyaniline and the reaction of the epoxide group on the hyperbranched polyorganosiloxane, dissaving structure has been introduced in the polyaniline chain, has proved the synthetic of polyaniline with dissaving structure.
The EDS data of table 1. polyaniline, hyperbranched polyorganosiloxane modified polyaniline
Referring to accompanying drawing 4, it is the electron scanning micrograph of polyaniline in the present embodiment, hyperbranched polyorganosiloxane modified polyaniline; Figure a is that polyaniline amplifies 20K, and figure b is that polyaniline amplifies 5K, and figure c is that the hyperbranched polyorganosiloxane modified polyaniline amplifies 20K, and figure d is that the hyperbranched polyorganosiloxane modified polyaniline amplifies 5K.Can see that polyaniline particle periphery is more clear regular, hyperbranched polyorganosiloxane modified polyaniline particle is fuzzyyer, and is coarse all around, shows that its crystallization is not too perfect, and hyperbranched polyorganosiloxane is successfully introduced in the polyaniline.
Referring to accompanying drawing 5, it is the X-ray diffractogram spectrogram of polyaniline, hyperbranched polyorganosiloxane modified polyaniline.As seen from the figure, four peaks are arranged in the X ray diffracting spectrum of polyaniline, 2 θ values are respectively 8.5 °, 15.0 °, 20.1 ° and 24.7 °, wherein 8.5 °, 24.7 ° to locate peak shape more sharp-pointed, it is mild to remain two place's peak shapes, show that polyaniline has certain crystallizing power, crystalline texture and amorphous structure coexistence.For the hyperbranched polyorganosiloxane modified polyaniline, the number of its diffraction peak, peak shape, the position that goes out the peak are all approximate with polyaniline, show that the hyperbranched polyorganosiloxane modified polyaniline has the phase structure similar to polyaniline; Yet each diffraction peak intensity has weakening to a certain degree, shows that crystallizing power descends, the crystalline form imperfection, and amorphous structure increases.
Referring to accompanying drawing 6, it is that the specific conductivity of polyaniline and hyperbranched polyorganosiloxane modified polyaniline under the room temperature is with the change curve of frequency.As seen from the figure, both specific conductivity-frequency curves are similar, and the electric conductivity size is close, show that the hyperbranched polyorganosiloxane modified polyaniline has kept the good electrical conductivity of polyaniline substantially.
Referring to accompanying drawing 7, it is the thermogravimetric curve (TGA) of polyaniline and hyperbranched polyorganosiloxane modified polyaniline.Initial heat decomposition temperature (Tdi) often is used to the thermostability of exosyndrome material, as seen from the figure, the Tdi of polyaniline and hyperbranched polyorganosiloxane modified polyaniline is respectively 282 ℃ and 360 ℃, show the thermostability of hyperbranched polyorganosiloxane modified polyaniline apparently higher than polyaniline, this mainly ascribes the existence of polysiloxane molecule chain to.
Can find out according to above performance data, compare with polyaniline, the hyperbranched polyorganosiloxane modified polyaniline of the present invention's preparation has better thermotolerance on the basis that keeps satisfactory electrical conductivity, can be used for preparing heat-resisting electro-conductive material, high dielectric constant material etc., have a extensive future.
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Prepare the hyperbranched polyorganosiloxane modified polyaniline by embodiment 1 technical scheme.
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 0.05g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.Its X-ray diffraction spectrum, Raman spectrogram, scanning electron microscope diagram and specific conductivity are respectively shown in Fig. 9,10,11 and 12.
Embodiment 3
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Prepare the hyperbranched polyorganosiloxane modified polyaniline by embodiment 1 technical scheme.
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 0.2g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.Its X-ray diffraction spectrum, Raman spectrogram, scanning electron microscope diagram are respectively shown in Fig. 9,10,11.
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Prepare the hyperbranched polyorganosiloxane modified polyaniline by embodiment 1 technical scheme.
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 0.1g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.Its X-ray diffraction spectrum, Raman spectrogram, scanning electron microscope diagram and specific conductivity are respectively shown in Fig. 9,10,11 and 12.
3, the preparation of comparative example 1 modified carbon nano-tube/epoxy resin composite material
Join in the flask with the 0.55g modified carbon nano-tube and with 100g Resins, epoxy (trade mark E-51), 60 ℃ of lower stirrings and after ultrasonic 1 hour, vacuum defoamation 30min, adding 4g 2-ethyl-4-methylimidazole, 10min is stirred in continuation, obtains uniform mixture; Mixture is poured in the mould, and vacuum defoamation 20min carries out thermofixation according to 80 ℃/2h+100 ℃/2h+120 ℃/2h and 140 ℃/4h technique, namely obtains modified carbon nano-tube/epoxy resin composite material.Its specific inductivity is seen respectively attached Figure 13 and 14 with frequency change figure, dielectric loss with frequency change figure.
4, the preparation of comparative example 2 carbon nano tube/epoxy resin composite materials
0.5g modified carbon nano-tube and 100g Resins, epoxy (trade mark E-51) are joined in the flask, and 60 ℃ of lower stirrings and after ultrasonic 1 hour, vacuum defoamation 30min adds the 4g 2-ethyl-4-methylimidazole, continues to stir 10min, obtains uniform mixture; Mixture is poured in the mould, and vacuum defoamation 20min carries out thermofixation according to 80 ℃/2h+100 ℃/2h+120 ℃/2h and 140 ℃/4h technique, namely obtains carbon nano tube/epoxy resin composite material.Its specific inductivity is seen respectively accompanying drawing 12 and 13 with frequency change figure, dielectric loss with frequency change figure.Its specific inductivity is seen respectively attached Figure 13 and 14 with frequency change figure, dielectric loss with frequency change figure.
Referring to accompanying drawing 9, it is the X-ray diffraction spectrogram of modified carbon nano-tube among carbon nanotube, the embodiment 1～4.As seen from the figure, behind the adding hyperbranched polyorganosiloxane modified polyaniline, the diffraction peak of carbon nanotube is to the skew of Small angle direction, and the sharp-pointed degree of peak shape reduces, and shows to have π-π effect between hyperbranched polyorganosiloxane modified polyaniline and the carbon nanotube.
Referring to accompanying drawing 10, it is the Raman spectrogram of modified carbon nano-tube among carbon nanotube, the embodiment 1～4.Compare with the spectrogram of carbon nanotube, the D band of modified carbon nano-tube and G band peak shape slightly broaden and skew have occured, and show to have π-π effect between hyperbranched polyorganosiloxane modified polyaniline and the carbon nanotube.
Referring to accompanying drawing 11, a among the figure, b, c, d figure are respectively the scanning electron microscope diagrams of modified carbon nano-tube among the embodiment 1～4.As seen from the figure, modified carbon nano-tube is applied in the hyperbranched polyorganosiloxane modified polyaniline equably, shows that hyperbranched polyorganosiloxane modified polyaniline provided by the invention can be by π-π effect dispersing Nano carbon tubes effectively.
Referring to accompanying drawing 12, it is modified carbon nano-tube, the AC conductivity histogram of carbon nanotube under the 10Hz frequency of embodiment 2,4 preparations.As seen from the figure, compare with carbon nanotube, modified carbon nano-tube has equal or higher electric conductivity, and this is because the large π system that hyperbranched polyorganosiloxane modified polyaniline and carbon nanotube form is conducive to the motion of electric charge, thereby is easy to obtain high conductivity.This application to modified carbon nano-tube has great meaning.
Referring to accompanying drawing 13, it is that the specific inductivity of matrix materials of the comparative example 1 that provides of the embodiment of the invention 4 and 2 preparations is with the change curve of frequency.As seen from the figure, modified carbon nano-tube/epoxy resin composite material is much higher than carbon nano tube/epoxy resin composite material at the specific inductivity of low frequency range, shows that modified carbon nano-tube has significant application prospect aspect the preparation high dielectric constant material.
Referring to accompanying drawing 14, it is that the dielectric loss of matrix materials of the comparative example 1 that provides of the embodiment of the invention 4 and 2 preparations is with the change curve of frequency.The dielectric loss of the carbon nano tube/epoxy resin composite material of comparative example 2 preparation depends on frequency strongly, has very high dielectric loss (for example 10 under low frequency
2The dielectric loss of the matrix material under the Hz is up to 350).And the dielectric loss of the modified carbon nano-tube/epoxy resin composite material of comparative example 1 preparation weakens greatly to the dependency of frequency, dielectric loss under the low frequency obviously reduces simultaneously, shows that modified carbon nano-tube has outstanding advantage aspect the preparation low-dielectric loss matrix material.Comprehensive accompanying drawing 12 adds a small amount of modified carbon nano-tube and can significantly improve the specific inductivity of matrix material and greatly reduce dielectric loss as can be known, has concurrently in preparation to have significant advantage aspect high-k, the low-dielectric loss matrix material.
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get the 30mL dehydrated alcohol and make solvent, to wherein adding 35g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2Protection, slowly dropwise to add 3.5g pH under the magnetic agitation condition be 2 H
2SO
4Solution; Dropwise, be warming up to 60 ℃ and continue reaction 4 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.Weight-average molecular weight is 7800.
Get respectively 1.9g aniline, 2.1g meta-aminotoluene, 3.5g ORTHO AMINO PHENOL SULPHONIC, and to wherein adding 300mLH
2SO
4Solution (0.1mol/L), N
2Under protection, 0～5 ℃ of condition, mechanical stirring 30min.Dropwise add subsequently 100mL Potassium Persulphate (0.6mol/L) solution, and vigorous stirring.After dropwising, be incubated 12 hours until reaction finishes, use respectively dilution heat of sulfuric acid, acetone, deionized water wash, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.Limiting viscosity is 0.33dL/g.
In the 50mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2Under protection, the 20 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.1g hyperbranched polyorganosiloxane and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 72 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 68.77%.Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
3=H/CH
3 R
2/R
4=H/SO
3H
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 0.05g hyperbranched polyorganosiloxane modified polyaniline are added in the 30mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 40min, add in the 80mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.
Embodiment 6
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get the 20mL dehydrated alcohol and make solvent, to wherein adding 23.6g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2Protection, slowly dropwise to add 2.2g pH under the magnetic agitation condition be 2 tosic acid solution; Dropwise, be warming up to 55 ℃ and continue reaction 6 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.
Get respectively 0.9g aniline, 1.3g gavaculine, 1.3g anthranilic acid, and to wherein adding 150mL dodecylbenzenesulfonic acid solution (0.2mol/L), N
2Under protection, 0～5 ℃ of condition, mechanical stirring 30min.Dropwise add subsequently 100mL ammonium persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 24 hours until reaction finishes, reaction solution is added breakdown of emulsion in the excessive methyl alcohol, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration after the filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.
In the 80mL dimethyl sulfoxide (DMSO), add 1.0g polyaniline, N
2Under protection, the 50 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.3g hyperbranched polyorganosiloxane and 0.01g hydrochloric acid and joins in this mixing solutions, continues to stir 5 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 72.73%.Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
3/R
2/R
4=H/COOH
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 0.1g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 40min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.
Embodiment 7
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get the 20mL dehydrated alcohol and make solvent, to wherein adding 23.6g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2Protection, slowly dropwise to add 2.2g pH under the magnetic agitation condition be 10 NaOH solution; Dropwise, be warming up to 50 ℃ and continue reaction 6 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.
Get respectively 1.9g aniline, 2.1g Ortho Toluidine, 3.5g m-sulfanilic acid, and to wherein adding 300mL camphorsulfonic acid solution (0.2mol/L), N
2Under protection, 0～5 ℃ of condition, mechanical stirring 45min.Dropwise add subsequently 100mL Potassium Persulphate (0.6mol/L) solution, and vigorous stirring.After dropwising, be incubated 5 hours until reaction finishes, with above-mentioned reacting liquid filtering, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.
In the 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2Under protection, the 20 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.2g hyperbranched polyorganosiloxane and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 72 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 68.33%.Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
3=H/SO
3H R
2/R
4=H/CH
3 
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 0.2g hyperbranched polyorganosiloxane modified polyaniline are added in the 40mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 90mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get the 25mL dehydrated alcohol and make solvent, to wherein adding 23.6g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2Protection, slowly dropwise to add 2.2g pH under the magnetic agitation condition be 10 KOH solution; Dropwise, be warming up to 55 ℃ and continue reaction 5 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.
Get 1.4g aniline, 1.8g2, the 3-xylidine, and to wherein adding 150mL tosic acid solution (0.2mol/L), N
2Under protection, 0～5 ℃ of condition, mechanical stirring 30min.Dropwise add subsequently 100mL ammonium persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 6 hours until reaction finishes, use respectively tosic acid solution, acetone, deionized water wash, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.
In the 45mL dimethyl sulfoxide (DMSO), add the above-mentioned polyaniline of 0.5g, N
2Under protection, the 50 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.1g hyperbranched polyorganosiloxane and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 5 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 71.92%.Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
2/R
3/R
4=H/CH
3 
2, the preparation of modified carbon nano-tube
1g Single Walled Carbon Nanotube and 0.5g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 40min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get the 30mL dehydrated alcohol and make solvent, to wherein adding 28.3g 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, at room temperature, N
2Protection, slowly dropwise to add 2.2g pH under the magnetic agitation condition be 10 tetramethyl ammonium hydroxide solution; Dropwise, be warming up to 60 ℃ and continue reaction 4 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.
Get respectively 2.8g aniline, and to wherein adding 150mL thionamic acid solution (0.2mol/L), N
2Under protection, 0～5 ℃ of condition, mechanical stirring 30min.Dropwise add subsequently 100mL ammonium persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 6 hours until reaction finishes, use respectively thionamic acid solution, acetone, deionized water wash, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.
In the 45mL dimethyl sulfoxide (DMSO), add 0.5g polyaniline, N
2Under protection, the 25 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.1g hyperbranched polyorganosiloxane and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 68.25%.Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
2/R
3/R
4=H
2, the preparation of modified carbon nano-tube
1g Single Walled Carbon Nanotube and 1g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get the 30mL dehydrated alcohol and make solvent, to wherein adding 11.8g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2Protection, slowly dropwise to add 1.2g pH under the magnetic agitation condition be 10 tetraethyl ammonium hydroxide solution; Dropwise, be warming up to 60 ℃ and continue reaction 4 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.
Get the 3.3g Ortho Toluidine, and to wherein adding 150mL beta-naphthalenesulfonic-acid (0.2mol/L), N
2Under protection, 0～5 ℃ of condition, mechanical stirring 30min.Dropwise add subsequently 100mL ammonium persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 6 hours until reaction finishes, will use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration behind the above-mentioned reacting liquid filtering, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.
In the 45mL dimethyl sulfoxide (DMSO), add the above-mentioned polyaniline of 0.5g, N
2Under protection, the 25 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.1g hyperbranched polyorganosiloxane and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 73.48%.Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
3=H R
2/R
4=CH
3 
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 2g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.
Embodiment 11
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get 30mL ethanol and make solvent, to wherein adding 15.7g2-(3,4-epoxy cyclohexane alkyl) ethyl triethoxysilane, at room temperature, N
2Protection, slowly dropwise to add 1.2g pH under the magnetic agitation condition be 10 NaOH solution; Dropwise, be warming up to 50 ℃ and continue reaction 5 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.
Get respectively 1.9g aniline, 2.1g Ortho Toluidine, 3.1g m-sulfanilic acid, and to wherein adding 300mL nitric acid (0.2mol/L), N
2Under protection, 0～5 ℃ of condition, mechanical stirring 30min.Dropwise add subsequently 100mL ammonium persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 6 hours until reaction finishes, will use respectively dilute nitric acid solution, acetone, deionized water wash, suction filtration behind the above-mentioned reacting liquid filtering, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.
In the 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2Under protection, the 20 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.2g hyperbranched polyorganosiloxane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 72 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 69.55%.Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
3=H/SO
3H R
2/R
4=H/CH
3 
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 5g hyperbranched polyorganosiloxane modified polyaniline are added in the 40mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 90mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.
Embodiment 12
1, the preparation of hyperbranched polyorganosiloxane modified polyaniline
Get 30mL ethanol and make solvent, to wherein adding 11.8g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2Protection, slowly dropwise to add 1.2g pH under the magnetic agitation condition be 10 NaOH solution; Dropwise, be warming up to 50 ℃ and continue reaction 5 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane that contains epoxy group(ing) of transparent thickness.
Get respectively 2.8g aniline, 3.3g Ortho Toluidine, and to wherein adding 300mL perchloric acid solution (0.2mol/L), N
2Under protection, 0～5 ℃ of condition, mechanical stirring 30min.Dropwise add subsequently 100mL ammonium persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 6 hours until reaction finishes, will use respectively rare perchloric acid solution, acetone, deionized water wash, suction filtration behind the above-mentioned reacting liquid filtering, and 50 ℃ of lower vacuum-dryings 24 hours, obtain polyaniline.
In the 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2Under protection, the 25 ° of C conditions, mechanical stirring 30min fully dissolves it, gets 0.2g hyperbranched polyorganosiloxane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.Reaction adds reaction solution in the excessive methyl alcohol after finishing, repetitive scrubbing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the hyperbranched polyorganosiloxane modified polyaniline, productive rate is 71.84%.Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
3=H R
2/R
4=H/CH
3 
2, the preparation of modified carbon nano-tube
1g carbon nanotube and 10g hyperbranched polyorganosiloxane modified polyaniline are added in the 50mL dimethyl sulfoxide (DMSO), behind 25 ℃ of lower stirrings and the ultrasonic 20min, add in the 100mL methyl alcohol and precipitate, suction filtration and washing, and 50 ℃ of lower vacuum-dryings 24 hours, obtain modified carbon nano-tube.
Claims (5)
1. the preparation method of a modified carbon nano-tube is characterized in that comprising the steps:
(1) at N
2Protection is lower, in mass ratio, 10 parts of polyanilines is dissolved in 500～1000 parts of dimethyl sulfoxide (DMSO), obtains polyaniline solutions; In polyaniline solutions, dropwise add 1～3 part and contain the hyperbranched polyorganosiloxane of epoxy group(ing) and 0.05～0.1 part hydrochloric acid, under 20～50 ℃ temperature condition, stirred 5～72 hours; After reaction finished, washing, suction filtration were removed solvent, obtain the hyperbranched polyorganosiloxane modified polyaniline;
(2) in mass ratio, the hyperbranched polyorganosiloxane modified polyaniline of 0.5 part carbon nanotube and 0.025～5 part is joined in 15～25 parts of dimethyl sulfoxide (DMSO), stir and supersound process 20～40min obtains reaction product; To precipitate in 40～50 parts of methyl alcohol of reaction product adding, suction filtration and washing obtain modified carbon nano-tube.
2. a kind of modified carbon nano-tube according to claim 1 and preparation method thereof, it is characterized in that: described carbon nanotube is single wall or multi-walled carbon nano-tubes, or its combination.
3. the preparation method of a kind of modified carbon nano-tube according to claim 1, it is characterized in that: described polyaniline is the polymkeric substance of phenyl amines monomer.
4. the preparation method of a kind of modified carbon nano-tube according to claim 3, it is characterized in that: the polymkeric substance of described phenyl amines monomer is aniline, Ortho Toluidine, m-sulfanilic acid, 2, the homopolymer of 3-xylidine, meta-aminotoluene, ORTHO AMINO PHENOL SULPHONIC, anthranilic acid, gavaculine, or the multipolymer of their arbitrary combination.
5. modified carbon nano-tube that obtains by preparation method claimed in claim 1.
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| CN109775689A (en) * | 2018-12-12 | 2019-05-21 | 深圳烯湾科技有限公司 | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application |
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| CN109775689A (en) * | 2018-12-12 | 2019-05-21 | 深圳烯湾科技有限公司 | Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application |
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