CN102746514B - Hyper branched polysiloxane modified polyaniline (PANI) and preparation method thereof - Google Patents
Hyper branched polysiloxane modified polyaniline (PANI) and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hyper branched polysiloxane modified PANI and a preparation method thereof. The method includes dissolving the PANI in dimethyl sulfoxide under the protection of N2; adding dropwisely the hyper branched polysiloxane which contains epoxy groups and adding in hydrochloric acid; reacting at a temperature of 20 DEG C to 50 DEG C; and obtaining the hyper branched polysiloxane modified PANI after washing and leaching. The product has better heat resistance and solubility on the premise that good conductivity of the PANI is maintained, has abundant active reaction groups simultaneously, and has a bright application prospect in various aspects such as further modification and application, research and development of novel high polymer materials and modification, high performance and multi-functionalization of polymers. The preparation method has the advantages that the operation process is simple, the yield can reach 68%-74%, sources of raw materials are rich, and the applicability is wide.
Description
Technical field
The present invention relates to a kind of organic high molecular compound and preparation method thereof, particularly a kind of modified polyaniline and preparation method thereof.
Background technology
Polyaniline is a kind of intrinsic conducting polymer being widely studied, and after proton doping or oxidizing reaction, can demonstrate electroconductibility.Polyaniline synthesis technique is simple, cheap and easy to get, have good environmental stability, granule-morphology is controlled, with the feature such as other macromolecular material consistencies are good.Along with the progress of polyaniline synthetic technology, its production efficiency improves constantly, and price also progressively reduces, for conduct a research on a large scale and application provide may.
Closely the result of the large quantity research of Chinese scholars expansion p-poly-phenyl amine decades shows, thermostability and the solvability of polyaniline remain to be further improved, to meet the demand of modern industry to functional materials.Therefore, polyaniline molecule is optimized the important content that modification becomes polyaniline research and development.
Before the present invention makes, Chinese invention patent (CN 100523048 C) discloses the preparation method of the polyaniline grafted multipolymer of a kind of water-soluble self-doping, it by polyaniline grafted on styrene sulfonic acid and amino cinnamic multipolymer, the graft copolymer solvability forming is better, can prevent that doping agent from moving and causing being separated in wider pH range.But the method complex synthetic route, but the not high the method synthesis step of productive rate is more, and the productive rate of the first step is only 40%, limited greatly its industrial applicability; In addition, on molecular chain, there is more sulfonic acid group, reduced to a certain extent the thermal characteristics of material.
Chinese invention patent (CN 101643544 B) discloses a kind of sulfonated polyaniline and preparation method thereof, and it is the segmented copolymer with sulfonic aniline segment and Oligoanilines, has good electroconductibility and thermotolerance.But this multipolymer is thread-like molecule, contained active function groups kind and limited amount, structure is single, is difficult to meet the requirement of modern industry to material multifunction.
Chinese invention patent (CN 102300907 A) discloses the preparation method of a kind of polyaniline addition prepolymer, polyaniline grafted polymkeric substance, it obtains two keys by polyaniline and containing glycidyl or containing isocyanate group (methyl) acrylate reactions, obtain polyaniline grafted polymkeric substance with another double bond containing monomer copolymerization again, and be further cross-linked into reticulated structure.But the polymkeric substance of grafting is the esters of acrylic acid that thermal degradation temperature is lower, will inevitably cause this polyaniline grafted polyalcohol integral thermal characteristics to decline; The site of adulterating in reaction process is less, causes specific conductivity lower.
By above-mentioned prior art, can be seen, current polyaniline-modified technology can only be improved certain or some deficiency of polyaniline substantially, and be difficult to adopt simple preparation method, on the basis of the original good electroconductibility of basic maintenance polyaniline, improve thermostability and the solvability of polyaniline simultaneously.Therefore, high-performance poly aniline of development of new and preparation method thereof is 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 integrated polyaniline, hyperbranched polyorganosiloxane molecular structure and performance advantage, and contains New Polyaniline of active group and preparation method thereof.
Realize the preparation method that technical scheme that the object of the invention adopts is to provide a kind of hyperbranched polyorganosiloxane modified polyaniline, comprise the steps: at N
2under protection, in mass ratio, 10 parts of polyanilines are dissolved in 500～1000 parts of dimethyl sulfoxide (DMSO), obtain polyaniline solutions; In polyaniline solutions, dropwise add 1～3 part containing hyperbranched polyorganosiloxane and 0.05～0.1 part of hydrochloric acid of epoxy group(ing), under the temperature condition of 20～50 ℃, stir 5～72 hours; After reaction finishes, washing, suction filtration, remove solvent, obtains hyperbranched polyorganosiloxane modified polyaniline.
The preparation method of polyaniline of the present invention, at N
2under protection, in molar ratio, by the aqueous solution of 1 part of phenyl amines monomer and 0.5～1 part of dopant acid; In temperature, be, under the agitation condition of 0～5 ℃, in molar ratio, to drip the aqueous solution of 1 part of initiator; After dropwising, react 5～24 hours, more respectively with doping aqueous acid, acetone, deionized water wash, through suction filtration, after being dried, obtain polyaniline.
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.
Described dopant acid is hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, thionamic acid, tosic acid, beta-naphthalenesulfonic-acid, camphorsulfonic acid or Witco 1298 Soft Acid.
Described initiator is ammonium persulphate or Potassium Persulphate.
The preparation method of the described hyperbranched polyorganosiloxane containing epoxy group(ing), in molar ratio, 11～16 parts of distilled water are mixed with 10 parts of trialkoxy silanes containing epoxide group, add 30～60 parts of solvent dehydrated alcohols, more slowly drip 0.001～0.003 part of catalyzer under agitation condition; After dropwising, be warming up to 50～60 ℃, react after 4～7 hours, through washing, dry, obtain the hyperbranched polyorganosiloxane containing 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 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.
Technical solution of the present invention also provides a kind of hyperbranched polyorganosiloxane modified polyaniline obtaining by above-mentioned preparation method.
Compared with prior art, the obtained beneficial effect of the present invention is:
1, the present invention utilizes the feature of hyperbranched polyorganosiloxane space multistory globosity, through reaction, at many polyaniline chains of end chemical graft of hyperbranched polyorganosiloxane, form space higly branched chain structure, but not single simple linear polymer chain has guaranteed that modified polyaniline still has high electric conductivity.
2, the existence of hyperbranched polyorganosiloxane is given modified polyaniline and is had a large amount of active reactive groups and quantitatively increase doubly, for the further changing-nature and application of polyaniline, research and development, polymer modification and the high performance of novel high polymer material, the aspect such as multiple functionalized have huge application prospect.
3, outstanding thermotolerance and the good solubility of hyperbranched polyorganosiloxane that the prepared hyperbranched polyorganosiloxane modified polyaniline of the present invention is integrated, therefore has thermotolerance and the solvability that is better than unmodified polyaniline.
4, the preparation method of hyperbranched polyorganosiloxane modified polyaniline provided by the invention have that operating procedure is simple, productive rate up to 68～74%, starting material source is abundant, suitability is wide feature.
Accompanying drawing explanation
Fig. 1 is the structural representation of the hyperbranched polyorganosiloxane modified polyaniline that provides of the embodiment of the present invention 1;
Fig. 2 is the infrared spectrum of hyperbranched polyorganosiloxane in the embodiment of the present invention 1, polyaniline, hyperbranched polyorganosiloxane modified polyaniline;
Fig. 3 is the ultraviolet-visible light spectrogram of polyaniline in the embodiment of the present invention 1, hyperbranched polyorganosiloxane modified polyaniline;
Fig. 4 is polyaniline in the embodiment of the present invention 1, hyperbranched polyorganosiloxane modified polyaniline
13c nmr spectrum;
Fig. 5 is the scanning electron microscope diagram of polyaniline in the embodiment of the present invention 1, hyperbranched polyorganosiloxane modified polyaniline;
Fig. 6 is the X-ray diffraction spectrogram of polyaniline in the embodiment of the present invention 1, hyperbranched polyorganosiloxane modified polyaniline;
Fig. 7 is the specific conductivity graphic representation of polyaniline in the embodiment of the present invention 1, hyperbranched polyorganosiloxane modified polyaniline;
Fig. 8 is the thermogravimetric curve figure of polyaniline in the embodiment of the present invention 1, hyperbranched polyorganosiloxane modified polyaniline;
Fig. 9 is that polyaniline in the embodiment of the present invention 1, hyperbranched polyorganosiloxane modified polyaniline are dissolved in respectively ten kinds of digital photograph figure in solvent, in figure, solvent is from left to right followed successively by dimethyl sulfoxide (DMSO), DMF, N-Methyl pyrrolidone, tetrahydrofuran (THF), methylene dichloride, Glacial acetic acid, acetone, ethanol, tetracol phenixin and benzene;
Figure 10 is the transmitance histogram of polyaniline in the embodiment of the present invention 1, hyperbranched polyorganosiloxane modified polyaniline.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention will be further described.
Embodiment 1
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 20mL dehydrated alcohol and make solvent, add wherein 23.6g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 2.2g pH under magnetic agitation condition be 2 HCl solution; Dropwise, be warming up to 50 ℃ and continue reaction 4 hours; After completion of the reaction, carry out underpressure distillation, obtain the hyperbranched polyorganosiloxane containing epoxy group(ing) of transparent thickness.Weight-average molecular weight 7500.
2, the preparation of 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 ℃ 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 ℃, polyaniline obtained.Limiting viscosity 0.32dL/g.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 45mL dimethyl sulfoxide (DMSO), add 0.5g polyaniline, N
2protection, 25
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 74.17%.
Referring to accompanying drawing 1, it is the structural representation of hyperbranched polyorganosiloxane modified polyaniline provided by the invention; In the present embodiment,
Referring to accompanying drawing 2, it is the infrared spectrum of hyperbranched polyorganosiloxane in the present embodiment, polyaniline, hyperbranched polyorganosiloxane modified polyaniline.What time following as seen from Figure 2: (1) hyperbranched polyorganosiloxane modified polyaniline has retained the skeleton structure of polyaniline, at 1090～1180cm
-1place exists more by force compared with broad absorption band, is the charateristic avsorption band of Si-O-Si, shows that polyaniline is successfully connected to the periphery of hyperbranched polyorganosiloxane, and (2) are at 814 cm
-1there is weak epoxy absorption peak in place, although show amino on polyaniline can with in hyperbranched polyorganosiloxane epoxide group reacts, but hyperbranched polyorganosiloxane is spherical three-dimensional arrangement, sterically hindered larger, epoxide group can not complete reaction, for the further changing-nature and application of polyaniline, research and development, polymer modification and the high performance of novel high polymer material, multiple functionalized providing may.
Referring to accompanying drawing 3, it is the ultraviolet-visible light spectrogram of polyaniline in the present embodiment, hyperbranched polyorganosiloxane modified polyaniline.From scheming relatively, compare with polyaniline, all having there is strong blue-shifted phenomenon 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, super branched molecule is successfully introduced in polyaniline.
Referring to accompanying drawing 4, it is polyaniline and hyperbranched polyorganosiloxane modified polyaniline in the present embodiment
13c nmr spectrum.Can find with polyaniline curve comparison, in the spectrogram of hyperbranched polyorganosiloxane modified polyaniline, occur many new
13c fignal center, shows that hyperbranched polyorganosiloxane is introduced in polyaniline with amino reacting by epoxy group(ing).
Referring to table 1, it is the ultimate analysis EDS table of the terpolymer aniline that makes of the present embodiment and hyperbranched polyorganosiloxane modified polyaniline.From EDS data, in aniline copolymer, in the atomic percentage conc of C, N, S, O and the monomer that adds, each constituent content is similar, shows that it is the terpolymer of aniline really; In hyperbranched polyorganosiloxane modified polyaniline, Si, O content increase, C, N, S content slightly reduce, show to react with the epoxide group on hyperbranched polyorganosiloxane by the amino on polyaniline, dissaving structure has been introduced in polyaniline chain, has proved polyaniline synthetic with dissaving structure.
The EDS data of table 1. polyaniline, hyperbranched polyorganosiloxane modified polyaniline
Referring to accompanying drawing 5, 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 hyperbranched polyorganosiloxane modified polyaniline amplifies 20K, and figure d is that hyperbranched polyorganosiloxane modified polyaniline amplifies 5K.By relatively seeing, polyaniline particle periphery is more clear regular, and hyperbranched polyorganosiloxane modified polyaniline particle is fuzzyyer, and surrounding is coarse, shows that its crystallization is not too perfect, and hyperbranched polyorganosiloxane is successfully introduced in polyaniline.
Referring to accompanying drawing 6, it is the X-ray diffractogram spectrogram of polyaniline, hyperbranched polyorganosiloxane modified polyaniline, as seen from the figure, in the X ray diffracting spectrum of polyaniline, there are four peaks, 2 θ values are respectively 8.5 °, 15.0 °, 20.1 ° and 24.7 °, and wherein 8.5 °, 24.7 ° to locate peak shape more sharp-pointed, remains two place's peak shapes mild, show that polyaniline has certain crystallizing power, crystalline texture and amorphous structure coexist.For hyperbranched polyorganosiloxane modified polyaniline, the number of its diffraction peak, peak shape, the position that goes out peak are all approximate with polyaniline, show that hyperbranched polyorganosiloxane modified polyaniline has the phase structure similar to polyaniline; Yet each diffraction peak intensity has weakening to a certain degree, show that crystallizing power declines, crystalline form imperfection, amorphous structure increases.
Referring to accompanying drawing 7, it is that the specific conductivity of polyaniline and hyperbranched polyorganosiloxane modified polyaniline under room temperature is with the change curve of frequency.As seen from the figure, both specific conductivity-frequency curves are similar, and electric conductivity size is close, show that hyperbranched polyorganosiloxane modified polyaniline has kept the good electrical conductivity of polyaniline substantially.
Referring to accompanying drawing 8, it is the TGA curve of polyaniline and hyperbranched polyorganosiloxane modified polyaniline.Initial heat decomposition temperature (Tdi) is often 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 that the thermostability of hyperbranched polyorganosiloxane modified polyaniline is apparently higher than polyaniline, this mainly ascribes the existence of polysiloxane molecule chain to.
Referring to accompanying drawing 9, it is that polyaniline, hyperbranched polyorganosiloxane modified polyaniline are dissolved in respectively ten kinds of digital photographs in solvent, in figure, from left to right, solvent is followed successively by dimethyl sulfoxide (DMSO), DMF, N-Methyl pyrrolidone, tetrahydrofuran (THF), methylene dichloride, Glacial acetic acid, acetone, ethanol, tetracol phenixin and benzene.From photo, polyaniline can be dissolved in the solvent (as dimethyl sulfoxide (DMSO), DMF, N-Methyl pyrrolidone) of strong polarity, is partially soluble in the relatively low tetrahydrofuran (THF) of polarity, and the solvability in residual solvent is poor.And the solvability of hyperbranched polyorganosiloxane modified polyaniline in each solvent improves, color burn, is apparent that most in tetrahydrofuran (THF), color by light blue change into dark blue, show after modification, the solubleness of hyperbranched polyorganosiloxane modified polyaniline in solvent increases.
Referring to accompanying drawing 10, it is polyaniline, the hyperbranched polyorganosiloxane modified polyaniline transmitance histogram in each solvent.Can find out, before and after modification, polyaniline transmitance in intensive polar solvent is lower, and in the lower solvent of polarity, transmitance is higher; In each solvent, the transmitance of hyperbranched polyorganosiloxane modified polyaniline is generally lower than polyaniline, and in tetrahydrofuran (THF) transmitance to reduce degree the most obvious, show that the solvability of hyperbranched polyorganosiloxane modified polyaniline is obviously better than the solvability of polyaniline.Deliquescent raising is owing to connecting hyperbranched polyorganosiloxane on polyaniline molecule chain, and amorphous structure increases, and makes solvent molecule ratio be easier to diffuse into hyperbranched polyorganosiloxane modified polyaniline intermolecular, has improved solvability.
According to above performance data, can find out, compare with polyaniline, hyperbranched polyorganosiloxane modified polyaniline prepared by the present invention is keeping on the basis of satisfactory electrical conductivity, there is better thermotolerance and solvability, can be used for preparing heat-resisting electro-conductive material, high dielectric constant material etc., have a extensive future.
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 30mL dehydrated alcohol and make solvent, add wherein 35g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 3.5g pH under magnetic agitation condition be 2 H
2sO
4solution; Dropwise, be warming up to 50 ℃ and continue reaction 5 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane containing epoxy group(ing) of transparent thickness.Weight-average molecular weight 7800.
2, the preparation of polyaniline
Get respectively 1.9g aniline, 2.1g Ortho Toluidine, 3.5g m-sulfanilic acid, and add wherein 300mLHCl solution (0.2mol/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 6 hours until reaction finishes, use respectively dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 ℃, polyaniline obtained.Limiting viscosity 0.33dL/g.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2protection, 20
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 70.39%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
?。
Embodiment 3
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 20mL dehydrated alcohol and make solvent, add wherein 23.6g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 2.2g pH under magnetic agitation condition be 2 HCl solution; Dropwise, be warming up to 50 ℃ and continue reaction 4 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get respectively 0.9g aniline, 1.1g Ortho Toluidine, 1.7g m-sulfanilic acid, and add wherein 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 5 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 50
℃lower vacuum-drying 24 hours, obtains polyaniline.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 80mL dimethyl sulfoxide (DMSO), add 1.0g polyaniline, N
2protection, 50
ounder C condition, mechanical stirring 30min fully dissolves it, gets 0.2g hyperbranched polyorganosiloxane and 0.01g hydrochloric acid and joins in this mixing solutions, continues to stir 5 hours.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 72.73%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
。
Embodiment 4
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 20mL dehydrated alcohol and make solvent, add wherein 23.6g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 2.2g pH under 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 containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get respectively 1.9g aniline, 2.1g Ortho Toluidine, 3.5g m-sulfanilic acid, and add wherein 300mL dodecylbenzenesulfonic 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, 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 ℃, polyaniline obtained.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2protection, 25
ounder C condition, 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 48 hours.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 68.33%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 25mL dehydrated alcohol and make solvent, add wherein 23.6g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 2.2g pH under magnetic agitation condition be 10 NaOH solution; Dropwise, be warming up to 55 ℃ and continue reaction 5 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get 2.8g aniline, and add wherein 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 dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and 50
℃lower vacuum-drying 24 hours, obtains polyaniline.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 45mL dimethyl sulfoxide (DMSO), add the above-mentioned polyaniline of 0.5g, N
2protection, 20
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 71.92%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
Embodiment 6
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 30mL dehydrated alcohol and make solvent, add wherein 28.3g 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, at room temperature, N
2protection, slowly dropwise to add 2.2g pH under magnetic agitation condition be 10 KOH solution; Dropwise, be warming up to 60 ℃ and continue reaction 4 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get respectively 0.9g aniline, 1.1g Ortho Toluidine, 1.7g m-sulfanilic acid, and add wherein 150mL camphorsulfonic 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 dilute hydrochloric acid solution, acetone, deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 ℃, polyaniline obtained.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 45mL dimethyl sulfoxide (DMSO), add 0.5g polyaniline, N
2protection, 25
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 68.25%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
Embodiment 7
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 30mL dehydrated alcohol and make solvent, add wherein 11.8g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 1.2g pH under magnetic agitation condition be 10 NaOH solution; Dropwise, be warming up to 60 ℃ and continue reaction 4 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get 3.3g Ortho Toluidine, and add wherein 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 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 ℃, polyaniline obtained.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 45mL dimethyl sulfoxide (DMSO), add the above-mentioned polyaniline of 0.5g, N
2protection, 25
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 73.48%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
Embodiment 8
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 30mL ethanol and make solvent, add wherein 15.7g2-(3,4-epoxy cyclohexane alkyl) ethyl triethoxysilane, at room temperature, N
2protection, slowly dropwise to add 1.2g pH under 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 containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get respectively 1.9g aniline, 2.1g Ortho Toluidine, 3.1g m-sulfanilic acid, and add wherein 300mL 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 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 ℃, polyaniline obtained.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2protection, 20
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 69.55%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
Embodiment 9
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 30mL ethanol and make solvent, add wherein 11.8g3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 1.2g pH under 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 containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get respectively 2.8g aniline, 3.3g Ortho Toluidine, and add wherein 300mLHCl 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 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 ℃, polyaniline obtained.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2protection, 25
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 71.84%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 30mL ethanol and make solvent, add wherein 11.8g3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 1.2g pH under 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 containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get respectively 2.8g aniline, 5.2g m-sulfanilic acid, and add wherein 300mLHCl 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 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 ℃, polyaniline obtained.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2protection, 25
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 73.69%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
Embodiment 11
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 30mL ethanol and make solvent, add wherein 11.8g 3-glycidyl ether oxygen base propyl trimethoxy silicane, at room temperature, N
2protection, slowly dropwise to add 1.2g pH under magnetic agitation condition be 10 tetramethyl ammonium hydroxide solution; Dropwise, be warming up to 50 ℃ and continue reaction 5 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get respectively 3.2g Ortho Toluidine, 5.2g m-sulfanilic acid, and add wherein 300mL HCl 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 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 ℃, polyaniline obtained.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2protection, 25
ounder C condition, 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.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 72.89%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
。
Embodiment 12
1, synthetic containing the hyperbranched polyorganosiloxane of epoxy group(ing)
Get 30mL ethanol and make solvent, add wherein 14.2g2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, at room temperature, N
2protection, slowly dropwise to add 1.3g pH under magnetic agitation condition be 10 tetramethyl ammonium hydroxide solution; Dropwise, be warming up to 50 ℃ and continue reaction 5 hours; Question response is complete, carries out underpressure distillation, obtains the hyperbranched polyorganosiloxane containing epoxy group(ing) of transparent thickness.
2, the preparation of polyaniline
Get respectively 2.8g aniline, 3.2g Ortho Toluidine, and add wherein 300mLHCl 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 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 ℃, polyaniline obtained.
3, the preparation of hyperbranched polyorganosiloxane modified polyaniline
In 80mL dimethyl sulfoxide (DMSO), add 1g polyaniline, N
2protection, 50
ounder C condition, 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 5 hours.After reaction finishes, reaction solution is added in excessive methyl alcohol, repetitive scrubbing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain hyperbranched polyorganosiloxane modified polyaniline, and productive rate is 74.03%.
The structural representation of hyperbranched polyorganosiloxane modified polyaniline is referring to accompanying drawing 1, wherein,
Claims (8)
1. a preparation method for hyperbranched polyorganosiloxane modified polyaniline, is characterized in that comprising the steps: at N
2under protection, in mass ratio, 10 parts of polyanilines are dissolved in 500～1000 parts of dimethyl sulfoxide (DMSO), obtain polyaniline solutions; In polyaniline solutions, dropwise add 1～3 part of hyperbranched polyorganosiloxane containing epoxy group(ing) and the hydrochloric acid of 0.05～0.1 part, under the temperature condition of 20～50 ℃, stir 5～72 hours; After reaction finishes, washing, suction filtration, remove solvent, obtains hyperbranched polyorganosiloxane modified polyaniline.
2. the preparation method of a kind of hyperbranched polyorganosiloxane modified polyaniline according to claim 1, is characterized in that: the preparation method of described polyaniline, and at N
2under protection, in molar ratio, by the aqueous solution of 1 part of phenyl amines monomer and 0.5～1 part of dopant acid; In temperature, be, under the agitation condition of 0～5 ℃, in molar ratio, to drip the aqueous solution of 1 part of initiator; After dropwising, react 5～24 hours, more respectively with doping aqueous acid, acetone, deionized water wash, through suction filtration, after being dried, obtain polyaniline.
3. the preparation method of a kind of hyperbranched polyorganosiloxane modified polyaniline according to claim 2, is characterized in that: described dopant acid is hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, thionamic acid, tosic acid, beta-naphthalenesulfonic-acid, camphorsulfonic acid or Witco 1298 Soft Acid.
4. the preparation method of a kind of hyperbranched polyorganosiloxane modified polyaniline according to claim 2, is characterized in that: described initiator is ammonium persulphate or Potassium Persulphate.
5. the preparation method of a kind of hyperbranched polyorganosiloxane modified polyaniline according to claim 1, it is characterized in that: the preparation method of the described hyperbranched polyorganosiloxane containing epoxy group(ing), in molar ratio, 11～16 parts of distilled water are mixed with 10 parts of trialkoxy silanes containing epoxide group, add 30～60 parts of solvent dehydrated alcohols, more slowly drip 0.001～0.003 part of catalyzer under agitation condition; After dropwising, be warming up to 50～60 ℃, react after 4～7 hours, through washing, dry, obtain the hyperbranched polyorganosiloxane containing epoxy group(ing).
6. the preparation method of a kind of hyperbranched polyorganosiloxane modified polyaniline according to claim 5, is characterized in that: described catalyzer is hydrochloric acid, sulfuric acid, tosic acid, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, sodium hydroxide or potassium hydroxide.
7. the preparation method of a kind of hyperbranched polyorganosiloxane modified polyaniline according to claim 5, 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 alkyl) ethyl triethoxysilane, or their arbitrary combination.
8. the hyperbranched polyorganosiloxane modified polyaniline obtaining by preparation method claimed in claim 1.
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