CN102875975B - Highly-branched-chain polyaniline modified carbon nanotube/thermosetting resin composite material and preparation method thereof - Google Patents
Highly-branched-chain polyaniline modified carbon nanotube/thermosetting resin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a highly-branched-chain polyaniline modified carbon nanotube/thermosetting resin composite material and a preparation method thereof. The preparation method comprises the following steps of: dissolving polyaniline in dimethyl sulfoxide, and dropwise adding trialkoxysilane containing epoxide group and hydrochloric acid in dimethyl sulfoxide to obtain organosilicone modified polyaniline; dissolving obtained organosilicone modified polyaniline in dimethyl sulfoxide, and then adding deionized water and hydrochloric acid into dimethyl sulfoxide to obtain highly-branched-chain polyaniline; adding highly-branched-chain polyaniline and carbon nanotubes into the carbon nanotube, and performing suction filter and washing on highly-branched-chain polyaniline and the carbon nanotubes which are settled in methyl alcohol, thus obtaining highly-branched-chain polyaniline modified carbon nanotubes which are mixed with thermocuring resin at a molten state; and curing the carbon nanotubes and the resin to obtain the highly-branched-chain polyaniline modified carbon nanotube/thermosetting resin composite material which has the characteristics of high dielectric constant and low dielectric loss. A conducting layer of the highly-branched-chain polyaniline wraps the surfaces of the carbon nanotubes, and the decentralized control on the carbon nanotubes and the control on dielectric properties of the composite material can be realized by adjusting the content of the surface wrapping layer. The preparation method is easy to implement and suitable for large-scale application.
Description
Technical field
The present invention relates to a kind of matrix material and preparation method thereof, particularly a kind of conductor/polymer composites and preparation method thereof.
Background technology
High-k, low-dielectric loss matrix material are current important functional materialss, and it has the effect of good preservation electric energy and uniform electric field, plays an important role in numerous sophisticated industries field.Carbon nano-tube/polymer composite material is the important form of preparing high dielectric constant material, closely decades, Chinese scholars was launched large quantity research to carbon nano-tube/polymer composite material, result shows that the dispersiveness of carbon nanotube is to affect the key factor that matrix material specific inductivity further improves, form coating layer outward at carbon nanotube and can effectively improve its dispersiveness, improve the dielectric properties of material.
Before the present invention makes; document (Cheng Yang; Yuanhua Lin, C.W.Nan.Modifiedcarbon nanotube composites with high dielectric constant, low dielectric loss andlarge energy density.CARBON; 47; 2009; 1096 – 1101) adopt the method for conversed phase micro emulsion copolymerization to prepare polystyrene based composites at the peripheral coated with conductive polypyrrole of carbon nanotube, research shows that in matrix material, carbon nanotube dispersed is even, and specific inductivity is higher with the stability of frequency.But matrix material specific inductivity prepared by the method is lower, at test frequency 10
2～10
7in scope, only have tens.Document (Yehai Yan, Jian Cui, Shuai Zhao, Jinfang Zhang, Jiwen Liu and Junmei Cheng.Interfacemolecular engineering of single-walled carbon nanotube/epoxy composites.J.Mater.Chem., 2012,22,1928.) reported that research shows containing amino pyrene derivative dispersing Nano carbon tubes effectively with preparing the matrix material taking epoxy resin as matrix containing amino pyrene derivative physics enveloped carbon nanometer tube.But the method enveloped carbon nanometer tube is higher containing amino pyrene derivative consumption, exceedes the consumption of carbon nanotube, can not give full play to self excellent properties of carbon nanotube.
Can be seen by above-mentioned prior art, current carbon nano-tube/polymer composite material technology of preparing can only be improved certain or some deficiencies substantially, and be difficult to adopt simple preparation method, only use a small amount of dispersion agent, on the basis of maintenance carbon nanotube good distribution, improve the specific inductivity of matrix material simultaneously and reduce dielectric loss.Therefore, the high-performance carbon nanotube dispersion agent of development of new and prepare novel carbon nano-tube/polymer composite material and be of great significance and value.
Summary of the invention
The deficiency existing in order to overcome prior art, the object of the present invention is to provide a kind of preparation method simple, performance is controlled, and has polyaniline-modified carbon nanotube/thermoset ting resin composite of higly branched chain of high-k, low-dielectric loss and preparation method thereof.
The technical scheme that realizes the object of the invention is to provide the preparation method of the polyaniline-modified carbon nanotube/thermoset ting resin composite of a kind of higly branched chain, comprises the steps:
1, at N
2under protection and stirring, in mass ratio, 10 parts of polyanilines are dissolved in 500～1000 parts of dimethyl sulfoxide (DMSO), dropwise add 1～3 part of trialkoxy silane and 0.05～0.1 part of hydrochloric acid containing epoxy group(ing), under 20～50 DEG C of conditions, react 5～72 hours, reaction finishes rear washing, suction filtration, obtains organic-silicon-modified polyaniline; Again 10 parts of organic-silicon-modified polyanilines are dissolved in 500～1000 parts of dimethyl sulfoxide (DMSO), dropwise add 10～15 parts of water and 0.05～0.1 part of hydrochloric acid, stirring reaction 10～72 hours under 20～50 DEG C of conditions, reaction finishes rear washing, suction filtration, obtains higly branched chain polyaniline;
2, in mass ratio, 0.5 part of carbon nanotube and 0.013～5 part of higly branched chain polyaniline are joined in 15～25 parts of dimethyl sulfoxide (DMSO), stir also supersound process 20～40min and obtain reaction product; Reaction product is added in 40～50 parts of methyl alcohol and precipitated, and suction filtration washing, obtain the polyaniline-modified carbon nanotube of higly branched chain;
3, in mass ratio, the thermal curable resin of 100 parts of molten states, 0.513～5.5 part of polyaniline-modified carbon nanotube of higly branched chain are mixed, through solidifying and obtaining the polyaniline-modified carbon nanotube/thermoset ting resin composite of a kind of higly branched chain.
In technical solution of the present invention, described heat-setting resin is self heat-setting resin; Or the resin system that jointly forms of resin that can not thermofixation by self and solidifying agent.The described trialkoxy silane containing 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.Described polyaniline is the polymkeric substance of phenyl amines monomer, as 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.
Technical solution of the present invention also comprises the polyaniline-modified carbon nanotube/thermoset ting resin composite of a kind of higly branched chain obtaining by above-mentioned preparation method.
Compared with prior art, the obtained beneficial effect of the present invention is:
1, the present invention, taking carbon nanotube as conductor, at the coated higly branched chain polyaniline in its surface, by the adjusting to higly branched chain polyaniline add-on, realizes the decentralised control of carbon nanotube and the control of matrix material dielectric properties thereof, and method is simple.
2, the side chain of higly branched chain polyaniline contains a large amount of phenyl ring, quinone ring structure, and this structure can be adsorbed on carbon nanotube with large π System forming π-π effect of carbon nano tube surface, reaches the object of dispersing Nano carbon tubes.Meanwhile, the existence of polysiloxane is given modified polyaniline and is had a large amount of active reactive groups and quantitatively increase doubly, for further reacting with resin matrix, realizes that carbon nanotube dispersed is stable to provide strong support.
3, the present invention, at many polyaniline chains of end chemical graft of polysiloxane, form space higly branched chain structure, but not single simple linear polymer chain guarantees that less add-on just can realize the good distribution to carbon nanotube.
4, the side chain of higly branched chain polyaniline is through the polyaniline of acid doping, has higher specific conductivity, can assist the specific inductivity that improves matrix material in dispersing Nano carbon tubes.
5, the prepared matrix material of higly branched chain polyaniline-coated carbon nanotube, in having high dielectric constant, greatly reduces the dielectric loss of matrix material, has overcome the drawback that prior art exists, and has realized the high performance of material.
6, the outstanding thermotolerance of polysiloxane that the prepared higly branched chain polyaniline of the present invention is integrated, therefore has the thermotolerance that is better than unmodified polyaniline.
Brief description of the drawings
Fig. 1 is the polyaniline prepared of the embodiment of the present invention 1, organic-silicon-modified polyaniline, the infrared spectrum of higly branched chain polyaniline;
Fig. 2 is the polyaniline prepared of the embodiment of the present invention 1, organic-silicon-modified polyaniline, the ultraviolet-visible spectrum of higly branched chain polyaniline;
Fig. 3 is the polyaniline prepared of the embodiment of the present invention 1, organic-silicon-modified polyaniline, higly branched chain polyaniline
1h-NMR(nucleus magnetic resonance) spectrogram;
Fig. 4 is the polyaniline prepared of the embodiment of the present invention 1, organic-silicon-modified polyaniline, the electron scanning micrograph of higly branched chain polyaniline;
Fig. 5 is the polyaniline prepared of the embodiment of the present invention 1, organic-silicon-modified polyaniline, the X-ray diffraction spectrogram of higly branched chain polyaniline;
Fig. 6 is the polyaniline prepared of the embodiment of the present invention 1, organic-silicon-modified polyaniline, the specific conductivity curve of higly branched chain polyaniline;
Fig. 7 is the polyaniline prepared of the embodiment of the present invention 1, organic-silicon-modified polyaniline, the thermogravimetric curve of higly branched chain polyaniline;
Fig. 8 is the structural representation of higly branched chain polyaniline provided by the invention;
Fig. 9 is the polyaniline-modified carbon nanotube of higly branched chain of the embodiment of the present invention 1～6 preparation, the X-ray diffraction spectrogram of unmodified carbon nanotube;
Figure 10 is the polyaniline-modified carbon nanotube of higly branched chain of the embodiment of the present invention 1～6 preparation, the Raman spectrogram of unmodified carbon nanotube;
Figure 11 is the scanning electron microscope diagram of the polyaniline-modified carbon nanotube of higly branched chain of the embodiment of the present invention 6 and 7 preparations;
Figure 12 is that the specific inductivity of the matrix material that provides of the embodiment of the present invention 2,3, comparative example is with the graphic representation of change of frequency;
Figure 13 is that the dielectric loss of the matrix material that provides of the embodiment of the present invention 2,3, comparative example is with the graphic representation of change of frequency.
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 higly branched chain polyaniline
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 DEG C 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 vacuum-drying 24 hours at 50 DEG C, polyaniline obtained, limiting viscosity 0.43dL/g.Its infrared spectrum, ultraviolet-visible light spectrogram,
1h nmr spectrum, scanning electronic microscope, X-ray diffraction spectrum, specific conductivity curve and thermogravimetric curve are respectively as shown in accompanying drawing 1,2,3,4,5,6 and 7.
In the dimethyl sulfoxide (DMSO) of 90mL, add 1g polyaniline, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.2g 3-glycidyl ether oxygen base propyl trimethoxy silicane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.Its infrared spectrum, ultraviolet-visible light spectrogram,
1h nmr spectrum, scanning electronic microscope, X-ray diffraction spectrum, specific conductivity curve and thermogravimetric curve are respectively as shown in accompanying drawing 1,2,3,4,5,6 and 7.
In the dimethyl sulfoxide (DMSO) of 90mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1.5g deionized water and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain polyaniline, productive rate is 75.32%, limiting viscosity 0.84dL/g.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 higly branched chain polyaniline prepared by the present embodiment, ultraviolet-visible light spectrogram,
1h nmr spectrum, scanning electronic microscope, X-ray diffraction spectrum, specific conductivity curve and thermogravimetric curve are respectively as shown in accompanying drawing 1,2,3,4,5,6 and 7.
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 0.025g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20min, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.Its X-ray diffraction spectrum, Raman spectrogram are respectively as shown in Fig. 9,10.
3, the preparation of the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain
Join in flask by polyaniline-modified 0.513g higly branched chain carbon nanotube and with 100g epoxy resin (trade mark E-51), at 60 DEG C, stirring is also after ultrasonic 1 hour, and vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, obtains the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain.
Referring to accompanying drawing 1, it is the polyaniline in the present embodiment, organic-silicon-modified polyaniline, the infrared spectrum of higly branched chain polyaniline.As seen from the figure, compared with polyaniline, 3400cm in organic-silicon-modified polyaniline
-1, 2900cm
-1, 2840cm
-1and 1100cm
-1the absorption peak at place strengthens, and shows in polyaniline amino by the epoxy ring-opening in 3-glycidyl ether oxygen base propyl trimethoxy silicane; 1050-1150cm in higly branched chain polyaniline
-1place is the absorption peak of Si-O-Si, show that the successful hydrolytic condensation of organic-silicon-modified polyaniline becomes higly branched chain structure, and contain in this higly branched chain molecule-the further changing-nature and application that OH is polyaniline, the research and development of novel high polymer material, polymer modification and high performance, multiple functionalized providing may.
Referring to accompanying drawing 2, it is the polyaniline in the present embodiment, organic-silicon-modified polyaniline, the uv-visible absorption spectra of higly branched chain polyaniline.As seen from the figure, compared with polyaniline, the absorbing wavelength of the absorption band that two intensity of organic-silicon-modified polyaniline and higly branched chain polyaniline are higher all moves to short wavelength's direction.Absorption band blue shift shows that the conjugated degree of polymkeric substance reduces, and the coplanarity of phenyl ring declines, and the amino of polyaniline reacts the organic-silicon-modified polyaniline generating with side group with epoxide group in 3-glycidyl ether oxygen base propyl trimethoxy silicane; The one-step hydrolysis of going forward side by side generates higly branched chain polyaniline.
Referring to accompanying drawing 3, it is polyaniline in the present embodiment, organic-silicon-modified polyaniline, higly branched chain polyaniline
1h nmr spectrum.Can find with polyaniline curve comparison, in organic-silicon-modified polyaniline, the spectrogram of higly branched chain polyaniline, occur many new
1h fignal center, show that 3-glycidyl ether oxygen base propyl trimethoxy silicane is successfully connected on polyaniline, and hydrolytic condensation becomes higly branched chain polyaniline.
Referring to table 1, it is the terpolymer aniline that makes of the present embodiment, organic-silicon-modified polyaniline, the ultimate analysis EDS table of higly branched chain polyaniline.From EDS data, in polyaniline, in the atomic percentage conc of C, N, S, O and the monomer that adds, each constituent content is similar, shows that polyaniline is the terpolymer of aniline really; In organic-silicon-modified polyaniline, Si, O content increase, and C, N, S content slightly reduce, and show that 3-glycidyl ether oxygen base propyl trimethoxy silicane has been introduced in polyaniline chain; In higly branched chain polyaniline, Si content further increases, and shows that the success of higly branched chain polyaniline is synthetic.
The EDS data of table 1. polyaniline, organic-silicon-modified polyaniline, polysiloxane-modified polyaniline
Referring to accompanying drawing 4, it is polyaniline in the present embodiment, organic-silicon-modified polyaniline, the electron scanning micrograph of higly branched chain polyaniline; Figure a, b are that polyaniline amplifies 20K, 5K, and figure c, d are that organic-silicon-modified polyaniline amplifies 20K, 5K, and figure e, f are that higly branched chain polyaniline amplifies 20K, 5K.By relatively seeing, polyaniline particle periphery is more clear regular, and organic-silicon-modified polyaniline, higly branched chain polyaniline particle are fuzzyyer, and surrounding is coarse, shows that its crystallization is not too perfect, and organosilicon, polysiloxane are successfully introduced in polyaniline.
Referring to accompanying drawing 5, it is the X-ray diffractogram spectrogram of polyaniline, organic-silicon-modified polyaniline, higly branched chain polyaniline, as seen from the figure, in the X ray diffracting spectrum of polyaniline, there are four peaks, wherein 8.5 °, 24.7 ° to locate peak shape more sharp-pointed, remain two place's peak shapes mild, show that polyaniline has certain crystallizing power.In organic-silicon-modified polyaniline, only have two Long Feng of place, and respectively to less angular deflection, peak shape is mild, show that organosilicon is introduced in polyaniline; In higly branched chain polyaniline, locate a stronger peak for 18.3 °, position is offset to Small angle, peak shape is mild, and 9.3 ° of diffraction peak intensities of locating are very weak, almost can ignore, show that organic-silicon-modified polyaniline success hydrolytic condensation becomes higly branched chain polyaniline, crystallinity declines.
Referring to accompanying drawing 6, it is that the specific conductivity of polyaniline under room temperature, organic-silicon-modified polyaniline, higly branched chain polyaniline is with the change curve of frequency.As seen from the figure, specific conductivity-frequency curve of three is similar, and electric conductivity size is close, shows that higly branched chain polyaniline has kept the good electrical conductivity of polyaniline substantially.
Referring to accompanying drawing 7, it is polyaniline, organic-silicon-modified polyaniline, the TGA curve of higly branched chain polyaniline.Initial heat decomposition temperature (Tdi) is often used to the thermostability of exosyndrome material, as seen from the figure, polyaniline, organic-silicon-modified polyaniline, the Tdi of higly branched chain polyaniline are respectively 282 DEG C, 153 DEG C, 333 DEG C, show that the thermostability of higly branched chain polyaniline is apparently higher than polyaniline, this mainly ascribes the existence of the good polysiloxane molecule of thermotolerance to.
Can find out according to above performance data, compared with polyaniline, higly branched chain polyaniline prepared by the present invention is keeping, on the basis of satisfactory electrical conductivity, having better thermotolerance, can be used for preparing heat-resisting electro-conductive material, high dielectric constant material etc., have a extensive future.
Embodiment 2
1, the preparation of higly branched chain polyaniline
Prepare higly branched chain polyaniline by embodiment 1 technical scheme.
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 0.033g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20min, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.Its X-ray diffraction spectrum, Raman spectrogram are respectively as shown in Fig. 9,10.
3, the preparation of the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain
Join in flask by polyaniline-modified 0.517g higly branched chain carbon nanotube and with 100g epoxy resin (trade mark E-51), at 60 DEG C, stirring is also after ultrasonic 1 hour, and vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, obtains the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain.Its specific inductivity is shown in respectively accompanying drawing 12 and 13 with change of frequency figure, dielectric loss with change of frequency figure.
Embodiment 3
1, the preparation of higly branched chain polyaniline
Prepare higly branched chain polyaniline by embodiment 1 technical scheme.
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 0.05g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20mi n, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.Its X-ray diffraction spectrum, Raman spectrogram are respectively as shown in Fig. 9,10.
3, the preparation of the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain
Join in flask by polyaniline-modified 0.525g higly branched chain carbon nanotube and with 100g epoxy resin (trade mark E-51), at 60 DEG C, stirring is also after ultrasonic 1 hour, and vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, obtains the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain.Its specific inductivity is shown in respectively accompanying drawing 12 and 13 with change of frequency figure, dielectric loss with change of frequency figure.
4, the preparation of comparative example
0.5g carbon nanotube and 100g epoxy resin (trade mark E-51) are joined in flask, and at 60 DEG C, stirring is also after ultrasonic 1 hour, and vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continues to stir 10min, obtains uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, obtains carbon nano tube/epoxy resin composite material.Its specific inductivity is shown in respectively accompanying drawing 12 and 13 with change of frequency figure, dielectric loss with change of frequency figure.
Referring to accompanying drawing 12, it is that the specific inductivity of the matrix material that provides of the embodiment of the present invention 2,3 and comparative example is with the change curve of frequency.As seen from the figure, add after a small amount of higly branched chain polyaniline, the specific inductivity of matrix material is greatly improved.Show to regulate the add-on of higly branched chain polyaniline can realize the control to matrix material specific inductivity.
Referring to accompanying drawing 13, it is that the dielectric loss of the matrix material that provides of the embodiment of the present invention 2,3 and comparative example is with the change curve of frequency.The dielectric loss of matrix material prepared by comparative example depends on frequency strongly, has very high dielectric loss (for example 10 under low frequency
2the dielectric loss of the matrix material under Hz is up to 350).Contrary with comparative example, the dielectric loss of the matrix material of embodiment 2,3 preparations weakens greatly to the dependency of frequency, and dielectric loss under low frequency obviously reduces, show that the polyaniline-modified carbon nanotube of higly branched chain has outstanding advantage preparing aspect low-dielectric loss matrix material.
Embodiment 4
1, the preparation of higly branched chain polyaniline
Prepare higly branched chain polyaniline by embodiment 1 technical scheme.
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 0.1g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20min, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.Its X-ray diffraction spectrum, Raman spectrogram are respectively as shown in Fig. 9,10.
3, the preparation of the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain
Join in flask by polyaniline-modified 0.55g higly branched chain carbon nanotube and with 100g epoxy resin (trade mark E-51), at 60 DEG C, stirring is also after ultrasonic 1 hour, and vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, obtains the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain.
Embodiment 5
1, the preparation of higly branched chain polyaniline
Prepare higly branched chain polyaniline by embodiment 1 technical scheme.
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 0.2g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20min, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.Its X-ray diffraction spectrum, Raman spectrogram are respectively as shown in Fig. 9,10.
3, the preparation of the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain
Join in flask by polyaniline-modified 0.6g higly branched chain carbon nanotube and with 100g epoxy resin (trade mark E-51), at 60 DEG C, stirring is also after ultrasonic 1 hour, and vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, obtains the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain.
Embodiment 6
1, the preparation of higly branched chain polyaniline
Prepare higly branched chain polyaniline by embodiment 1 technical scheme.
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 1g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20mi n, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.Its X-ray diffraction spectrum, Raman spectrogram and scanning electron microscope diagram are respectively as shown in Fig. 9,10 and 11.
3, the preparation of the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain
Join in flask by polyaniline-modified 1g higly branched chain carbon nanotube and with 100g epoxy resin (trade mark E-51), at 60 DEG C, stirring is also after ultrasonic 1 hour, and vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, obtains the polyaniline-modified carbon nano tube/epoxy resin composite material of higly branched chain.
Referring to accompanying drawing 9, it is the X-ray diffraction spectrogram of the polyaniline-modified carbon nanotube of higly branched chain in carbon nanotube, embodiment 1～6.As seen from the figure, add after higly branched chain polyaniline, the diffraction peak of carbon nanotube is to Small angle direction skew, and the sharp-pointed degree of peak shape reduces, and shows to exist between higly branched chain polyaniline and carbon nanotube π-π effect.
Referring to accompanying drawing 10, it is the Raman spectrogram of the polyaniline-modified carbon nanotube of higly branched chain in carbon nanotube, embodiment 1～6.Compared with the spectrogram of carbon nanotube, D band and the G of the polyaniline-modified carbon nanotube of higly branched chain are with peak shape slightly broaden and skew has occurred, and show to exist between higly branched chain polyaniline and carbon nanotube π-π effect.
Embodiment 7
1, the preparation of higly branched chain polyaniline
Get respectively 0.9g aniline, 1.1g Ortho Toluidine, 1.7g m-sulfanilic acid, and add wherein 75mLH
2sO
4solution (0.2mol/L), N
2under protection, 0～5 DEG C of condition, mechanical stirring 30min.Dropwise add subsequently 100mL Potassium Persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 12 hours until reaction finishes, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 DEG C, polyaniline obtained, limiting viscosity 0.44dL/g.
In the dimethyl sulfoxide (DMSO) of 90mL, add 1g polyaniline, N
2under protection, 20 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.2g 3-glycidyl ether oxygen base propyl trimethoxy silicane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 72 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 90mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 20 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1.5g deionized water and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 72 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain polyaniline, productive rate is 71.39%, limiting viscosity 0.88dL/g.
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 the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 2g higly branched chain polyaniline are added in 30mL dimethyl sulfoxide (DMSO), stir at 25 DEG C and ultrasonic 40min after, add in 80mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.Its scanning electron microscope diagram respectively as shown in figure 11.
3, the preparation of the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain
Polyaniline-modified 1.5g higly branched chain carbon nanotube and 100g bisphenol A cyanate ester are joined in flask, at 150 DEG C, stir after 2h, obtain uniform mixture; Mixture is poured into mould and at 140 DEG C, vacuumizes 0.5 hour, carry out thermofixation according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 220 DEG C/4h technique, obtain the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain.
Referring to accompanying drawing 11, a, the b figure in figure is respectively the scanning electron microscope diagram of the polyaniline-modified carbon nanotube of higly branched chain in embodiment 6,7.As seen from the figure, add higly branched chain polyaniline, carbon nanotube can be applied in higly branched chain polyaniline uniformly.
Above result shows, higly branched chain polyaniline provided by the invention can be by the effective dispersing Nano carbon tubes of π-π effect, under the less prerequisite of add-on, significantly improve the specific inductivity of matrix material and greatly reduce dielectric loss, realizing the high performance of matrix material.
Embodiment 8
1, the preparation of higly branched chain polyaniline
Get respectively 1.4g aniline, 2.6g m-sulfanilic acid, and add wherein 150mL dodecylbenzenesulfonic acid solution (0.2mol/L), N
2under protection, 0～5 DEG C 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 to breakdown of emulsion in excessive methyl alcohol, after filtration, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 DEG C, polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 90mL, add 1g polyaniline, N
2under protection, 50 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.2g 3-glycidyl ether oxygen base propyl trimethoxy silicane and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 5 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 90mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 50 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1.5g deionized water and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 10 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain polyaniline, productive rate is 70.33%.
Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
3=H/SO
3H R
2/R
4=H
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 0.1g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 40mi n, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.
3, the preparation of the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain
Polyaniline-modified 0.55g higly branched chain carbon nanotube and 100g bisphenol A cyanate ester are joined in flask, at 150 DEG C, stir after 2h, obtain uniform mixture; Mixture is poured into mould and at 140 DEG C, vacuumizes 0.5 hour, carry out thermofixation according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 220 DEG C/4h technique, obtain the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain.
Embodiment 9
1, the preparation of higly branched chain polyaniline
Get respectively 1.6g Ortho Toluidine, 2.6g m-sulfanilic acid, and add wherein 300mL dodecylbenzenesulfonic acid solution (0.1mol/L), N
2under protection, 0～5 DEG C of condition, mechanical stirring 45min.Dropwise add subsequently 100mL Potassium Persulphate (0.6mol/L) solution, and vigorous stirring.After dropwising, be incubated 8 hours until reaction finishes, above-mentioned reaction solution is added to breakdown of emulsion, filtration in excessive methyl alcohol, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 DEG C, polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 45mL, add 1g polyaniline, N
2under protection, 20 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.1g 3-glycidyl ether oxygen base propyl trimethoxy silicane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 72 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 45mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1g deionized water and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain polyaniline, productive rate is 72.74%.
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 the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 0.2g higly branched chain polyaniline are added in 40mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20mi n, add in 90mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.
3, the preparation of the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain
Polyaniline-modified 0.6g higly branched chain carbon nanotube and 100g bisphenol A cyanate ester are joined in flask, at 150 DEG C, stir after 2h, obtain uniform mixture; Mixture is poured into mould and at 140 DEG C, vacuumizes 0.5 hour, carry out thermofixation according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 220 DEG C/4h technique, obtain the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain.
Embodiment 10
1, the preparation of higly branched chain polyaniline
Get 2.8g aniline, and add wherein 150mL tosic acid solution (0.2mol/L), N
2under protection, 0～5 DEG C 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 dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 DEG C, polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 70mL, add 1g polyaniline, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.3g 3-glycidyl ether oxygen base propyl trimethoxy silicane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 70mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1.5g deionized water and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain 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
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 0.5g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 40mi n, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.
3, the preparation of the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain
Polyaniline-modified 0.75g higly branched chain carbon nanotube and 100g bisphenol A cyanate ester are joined in flask, at 150 DEG C, stir after 2h, obtain uniform mixture; Mixture is poured into mould and at 140 DEG C, vacuumizes 0.5 hour, carry out thermofixation according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 220 DEG C/4h technique, obtain the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain.
Embodiment 11
1, the preparation of higly branched chain polyaniline
Get respectively 0.9g aniline, 1.1g Ortho Toluidine, 1.7g m-sulfanilic acid, and add wherein 150mL beta-naphthalenesulfonic-acid solution (0.2mol/L), N
2under protection, 0～5 DEG C of condition, mechanical stirring 30min.Dropwise add subsequently 100mL Potassium Persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 24 hours until reaction finishes, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 DEG C, polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 90mL, add 1g polyaniline, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.2g 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 90mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1.5g deionized water and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain polyaniline, productive rate is 69.87%.
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 the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 1g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20mi n, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.
3, the preparation of the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain
By polyaniline-modified 1g higly branched chain carbon nanotube and 100g N, N '-4,4 '-diphenyl methane dimaleimide (BDM) and diallyl bisphenol (DBA) mixture (wherein weight ratio, BDM:DBA=1:0.85) join in flask, stir in 140 DEG C, obtain TiB2/bimaleimide resin mixture.The mixture obtaining is vacuumized to 0.5 hour at 140 DEG C, then be cured respectively and aftertreatment according to the technique of 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 230 DEG C/4h.After naturally cooling, obtain the polyaniline-modified carbon nanotube/bismaleimide resin composite material of higly branched chain.
Embodiment 12
1, the preparation of higly branched chain polyaniline
Get 3.3g meta-aminotoluene, and add wherein 150mL dodecylbenzenesulfonic acid solution (0.2mol/L), N
2under protection, 0～5 DEG C 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, above-mentioned reaction solution is added to breakdown of emulsion in excessive methyl alcohol, after filtration, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 DEG C, polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 90mL, add 1g polyaniline, N
2under protection, 50 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.1g 3-glycidyl ether oxygen base propyl trimethoxy silicane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 24 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 90mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1.5g deionized water and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain polyaniline, productive rate is 73.15%.
Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
3=CH
3 R
2/R
4=H
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 2g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20mi n, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.
3, the preparation of the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain
By polyaniline-modified 1.5g higly branched chain carbon nanotube and 100g N, N '-4,4 '-diphenyl methane dimaleimide (BDM) and diallyl bisphenol (DBA) mixture (wherein weight ratio, BDM:DBA=1:0.85) join in flask, stir in 140 DEG C, obtain TiB2/bimaleimide resin mixture.The mixture obtaining is vacuumized to 0.5 hour at 140 DEG C, then be cured respectively and aftertreatment according to the technique of 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 230 DEG C/4h.After naturally cooling, obtain the polyaniline-modified carbon nanotube/bismaleimide resin composite material of higly branched chain.
Embodiment 13
1, the preparation of higly branched chain polyaniline
Get respectively 0.9g aniline, 1.1g Ortho Toluidine, 1.7g m-sulfanilic acid, and add wherein 300mL thionamic acid (0.2mol/L), N
2under protection, 0～5 DEG C 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 after above-mentioned reacting liquid filtering, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 DEG C, polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 65mL, add 1g polyaniline, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.2g2-(3,4-epoxy cyclohexane base) ethyl triethoxysilane and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 65mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1g deionized water and 0.005g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain polyaniline, productive rate is 68.12%.
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 the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 5g higly branched chain polyaniline are added in 40mL dimethyl sulfoxide (DMSO), stir at 25 DEG C and ultrasonic 20min after, add in 90mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.
3, the preparation of the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain
By polyaniline-modified 3g higly branched chain carbon nanotube and 100g N, N '-4,4 '-diphenyl methane dimaleimide (BDM) and diallyl bisphenol (DBA) mixture (wherein weight ratio, BDM:DBA=1:0.85) join in flask, stir in 140 DEG C, obtain TiB2/bimaleimide resin mixture.The mixture obtaining is vacuumized to 0.5 hour at 140 DEG C, then be cured respectively and aftertreatment according to the technique of 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 230 DEG C/4h.After naturally cooling, obtain the polyaniline-modified carbon nanotube/bismaleimide resin composite material of higly branched chain.
Embodiment 14
1, the preparation of higly branched chain polyaniline
Get respectively 1.4g aniline, 1.8g2,3-xylidine, and add wherein 600ml HNO
3solution (0.1mol/L), N
2under protection, 0～5 DEG C of condition, mechanical stirring 30min.Dropwise add subsequently 100mL Potassium Persulphate (0.3mol/L) solution, and vigorous stirring.After dropwising, be incubated 18 hours until reaction finishes, will after above-mentioned reacting liquid filtering, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 DEG C, polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 85mL, add 1g polyaniline, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 0.3g 3-glycidyl ether oxygen base propyl trimethoxy silicane and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, organic-silicon-modified polyaniline obtained.
In the dimethyl sulfoxide (DMSO) of 85mL, add the organic-silicon-modified polyaniline of 1g, N
2under protection, 25 DEG C of conditions, mechanical stirring 30min fully dissolves it, gets 1.5g deionized water and 0.01g hydrochloric acid and dropwise joins in this mixing solutions, continues to stir 48 hours.After question response finishes, reaction solution is added to repetitive scrubbing, suction filtration in excessive methyl alcohol, and vacuum-drying 24 hours at 50 DEG C, obtaining higly branched chain polyaniline, productive rate is 71.84%.
Its structural representation is referring to accompanying drawing 8, wherein,
R
1/R
2=H/CH
3 R
3/R
4=H/CH
3
2, the preparation of the polyaniline-modified carbon nanotube of higly branched chain
1g carbon nanotube and 10g higly branched chain polyaniline are added in 50mL dimethyl sulfoxide (DMSO), at 25 DEG C, after stirring ultrasonic 20min, add in 100mL methyl alcohol and precipitate, suction filtration washing, and vacuum-drying 24 hours at 50 DEG C, obtain the polyaniline-modified carbon nanotube of higly branched chain.
3, the preparation of the polyaniline-modified carbon nanotube/cyanate ester resin composite material of higly branched chain
By polyaniline-modified 5.5g higly branched chain carbon nanotube and 100g N, N '-4,4 '-diphenyl methane dimaleimide (BDM) and diallyl bisphenol (DBA) mixture (wherein weight ratio, BDM:DBA=1:0.85) join in flask, stir in 140 DEG C, obtain TiB2/bimaleimide resin mixture.The mixture obtaining is vacuumized to 0.5 hour at 140 DEG C, then be cured respectively and aftertreatment according to the technique of 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 230 DEG C/4h.After naturally cooling, obtain the polyaniline-modified carbon nanotube/bismaleimide resin composite material of higly branched chain.
Claims (6)
1. a preparation method for the polyaniline-modified carbon nanotube/thermoset ting resin composite of higly branched chain, is characterized in that comprising the steps:
(1) at N
2under protection and stirring, in mass ratio, 10 parts of polyanilines are dissolved in 500～1000 parts of dimethyl sulfoxide (DMSO), dropwise add 1～3 part of trialkoxy silane and 0.05～0.1 part of hydrochloric acid containing epoxy group(ing), under 20～50 DEG C of conditions, react 5～72 hours, reaction finishes rear washing, suction filtration, obtains organic-silicon-modified polyaniline; Again 10 parts of organic-silicon-modified polyanilines are dissolved in 500～1000 parts of dimethyl sulfoxide (DMSO), dropwise add 10～15 parts of water and 0.05～0.1 part of hydrochloric acid, stirring reaction 10～72 hours under 20～50 DEG C of conditions, reaction finishes rear washing, suction filtration, obtains higly branched chain polyaniline;
(2) in mass ratio, 0.5 part of carbon nanotube and 0.013～5 part of higly branched chain polyaniline are joined in 15～25 parts of dimethyl sulfoxide (DMSO), stir also supersound process 20～40min and obtain reaction product; Reaction product is added in 40～50 parts of methyl alcohol and precipitated, and suction filtration washing, obtain the polyaniline-modified carbon nanotube of higly branched chain;
(3) in mass ratio, the thermal curable resin of 100 parts of molten states, 0.513～5.5 part of polyaniline-modified carbon nanotube of higly branched chain are mixed, through solidifying and obtaining the polyaniline-modified carbon nanotube/thermoset ting resin composite of a kind of higly branched chain.
2. the preparation method of the polyaniline-modified carbon nanotube/thermoset ting resin composite of a kind of higly branched chain according to claim 1, is characterized in that: described heat-setting resin is self heat-setting resin; Or the resin system that jointly forms of resin that can not thermofixation by self and solidifying agent.
3. the preparation method of the polyaniline-modified carbon nanotube/thermoset ting resin composite of a kind of higly branched chain according to claim 1, it is characterized in that: the described trialkoxy silane containing 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 base) ethyl triethoxysilane, or their arbitrary combination.
4. the preparation method of the polyaniline-modified carbon nanotube/thermoset ting resin composite of a kind of higly branched chain according to claim 1, is characterized in that: described polyaniline is the polymkeric substance of phenyl amines monomer.
5. the preparation method of the polyaniline-modified carbon nanotube/thermoset ting resin composite of a kind of higly branched chain according to claim 4, it is characterized in that: the polymkeric substance of described phenyl amines monomer is the homopolymer of aniline, Ortho Toluidine, m-sulfanilic acid, 23 dimethyl aniline, meta-aminotoluene, ORTHO AMINO PHENOL SULPHONIC, anthranilic acid, gavaculine or the multipolymer of their arbitrary combination.
6. the polyaniline-modified carbon nanotube/thermoset ting resin composite of the higly branched chain obtaining by preparation method claimed in claim 1.
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