CN102532538A - Size-controllable polypyrrole nano particle and preparation method thereof - Google Patents
Size-controllable polypyrrole nano particle and preparation method thereof Download PDFInfo
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- CN102532538A CN102532538A CN2011104483125A CN201110448312A CN102532538A CN 102532538 A CN102532538 A CN 102532538A CN 2011104483125 A CN2011104483125 A CN 2011104483125A CN 201110448312 A CN201110448312 A CN 201110448312A CN 102532538 A CN102532538 A CN 102532538A
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Abstract
The invention discloses a size-controllable polypyrrole nano particle and a preparation method thereof. The preparation method comprises the following steps of: dissolving pyrrole and an initiator into a first solvent to form blended solution of pyrrole monomer and the initiator; dissolving an oxidant into a second solvent to form oxidant solution; then mixing the blended solution of the pyrrole monomer and the initiator with the oxidant solution, swaying violently, standing, and after reaction is complete, carrying out centrifugation, washing, drying and the like; and finally, obtaining the size-controllable polypyrrole nano particle. According to the size-controllable polypyrrole nano particle and the preparation method thereof, the preparation step is simple, high in efficiency and high in controllability; the particle size of the obtained size-controllable polypyrrole nano particle is 80-600nm, and the electric conductivity of the obtained size-controllable polypyrrole nano particle is 10<-2>-10<-7>S/cm. The size-controllable polypyrrole nano particle and the preparation method thereof can be used for the application fields such as sensors, actuating devices, artificial muscles, overpotential containers, electrochromic color-changing windows, fuel cells, functional coatings and ultrafiltration membranes.
Description
Technical field
The invention belongs to the conducting polymer nano material preparing technical field, be specifically related to a kind of controllable size polypyrrole nano particle and preparation method thereof.
Background technology
Polypyrrole (polypyrrole; PPy) with plurality of advantages such as its good environmental stability, simple and easy synthetic and high conductivity by extensive concern (Wang L X; Li X G, Yang Y L. Preparation, properties and applications of polypyrroles [J]. Reactive and Functional Polymers; 2001,47 (2): 125-139.).The unique big π key of polypyrrole is given its unusual pme, electrochemical effect, electrochemical machinery actuating effect etc.; Simultaneously, the transmission of the unbound electron of polypyrrole molecular chain receives specific environment like the control of acidity, humidity, atmosphere and chemically bonded etc. and influence the size of its electric conductivity.Therefore; Polypyrrole all has huge application potential (Skotheim T A in many fields such as transmitter, actuating device, artificial-muscle, ultra-capacitor, electrochromic, fuel cell, functional coat, ultra-filtration membranes; Reynolds J R. Handbook of Conducting Polymers [B]. New York; USA:CRC Press, 2007.); And be expected to replace many traditional inorganic semiconductor materials to prepare various electronic components.
In general, polypyrrole all is to utilize chemistry and electrochemical polymerization to come synthetic; Under the few cases, can also synthesize polypyrrole with enzyme catalysis through light-initiated.Yet; The polypyrrole polymer that is formed by the big π key of conjugation has very strong chain rigidity; And intermolecular and molecular memory are at the intensive interaction of hydrogen bond; Cause polypyrrole insoluble molten, this has just caused the difficult processing of polypyrrole, poor mechanical property and can not biological degradation, these shortcomings greatly to limit its practical application at chemical detection and biomedical sector.
Therefore, it is most important to improve the processing characteristics of polypyrrole.With the polypyrrole nanometer, this has not only solved the unmanageable problem of conducting polymer, and might obtain that electric conductivity is higher, electrochemical activity is stronger, mechanical property is more excellent, show the conducting polymer composite of nano effect.For example, be applied to chemical sensor after polypyrrole processed nanofiber, on susceptibility and responsiveness, obviously be superior to the polypyrrole material of its macro-size.Can predict, nanometer polypyrrole not only can be coated on the electrode very equably, has solved the unmanageable problem of polypyrrole effectively, and its nano effect that brings such as high specific surface area etc., makes it on biochemical sensor, must show special advantages.
Therefore, the compound method that seek a kind of economic actual effect, has good yield and a controllable size polypyrrole nano particle has not only solved the difficult problem of polypyrrole poor in processability, has strengthened the functional of polypyrrole self, and has expanded its range of application.
Summary of the invention
The objective of the invention is in order to overcome the deficiency of the poor processability that conductive polymers in the prior art exists, and propose a kind of controllable size polypyrrole nano particle and preparation method thereof.
Technical scheme of the present invention
A kind of controllable size polypyrrole nano particle is about to pyrrole monomer and initiator and is dissolved in first kind of solvent formation pyrrole monomer and initiator blend solution; Oxygenant is dissolved in second kind of solvent forms oxidizing agent solution; Again with initiator solution and pyrrole monomer blend solution with acutely rock after oxidizing agent solution mixes moments later standing and reacting fully after, carry out centrifugal, washing, drying etc., finally obtaining particle diameter is 80～600nm, electric conductivity is 10
-2～10
-7A kind of controllable size polypyrrole nano particle of S/cm;
Wherein, described initiator is 2,4-diamino-diphenyl amine;
Described first kind of solvent is methyl alcohol, ethanol or Virahol;
Described oxygenant is that Youxiaolin, ydrogen peroxide 50, ammonium persulphate, SRM 935a, FERRIC CHLORIDE ANHYDROUS or ydrogen peroxide 50/dichloride are ferrous, is preferably ammonium persulphate, SRM 935a, FERRIC CHLORIDE ANHYDROUS;
Described second solvent is that water or concentration are hydrochloric acid, nitric acid, perchloric acid or the camphorsulfonic acid of 1.0mol/L;
Described pyrrole monomer and initiator 2, the mol ratio of 4-diamino-diphenyl amine is 9～49:1;
Described pyrrole monomer and oxygenant mol ratio are 0.2～2:1.
The preparation method of above-mentioned a kind of controllable size polypyrrole nano particle specifically may further comprise the steps:
(1), with pyrrole monomer and 2,4-diamino-diphenyl amine solvent forms pyrrole monomer and initiator blend solution in first kind of solvent;
Described first solvent is methyl alcohol, ethanol or Virahol;
(2), oxygenant is dissolved in second kind of solvent, the formation oxidizing agent solution;
Described second kind of solvent is hydrochloric acid, nitric acid, camphorsulfonic acid or the high chloro acid solution that water or concentration are respectively 1.0mol/L;
(3), the pyrrole monomer of step (1) gained and the oxidizing agent solution of initiator blend solution and step (2) gained are cooled to 0 respectively
oC, short mix is acutely rocked about 10s with mixed solution then, obtains reaction solution behind the placing response 24h then;
(4), the control rotating speed was 4500r/min after the reaction solution of step (3) gained took out; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the mixing solutions of formed water of 9:1 and methyl alcohol washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again; Wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity; Be that drying obtained the polypyrrole nano particle after 7 days under the condition of 0.09MPa in control vacuum tightness under 50 ℃ then.
In the preparation process of above-mentioned a kind of controllable size polypyrrole nano particle, control the size of nano particle through regulating sour kind, oxidant type and initiator content, the polypyrrole nano particle diameter of final gained is 80～600nm, and electric conductivity is 10
-2～10
-7S/cm can be used for such as Application Areass such as transmitter, actuating device, artificial-muscle, ultra-capacitor, electrochromic, fuel cell, functional coat, ultra-filtration membranes.
In the preparation process of above-mentioned a kind of controllable size polypyrrole nano particle, 2,4-diamino-diphenyl amine has play a part very crucial in forming the polypyrrole nanometer ball.
The preparation method of prior art can only obtain the reunion polypyrrole of particle for micron, and the present invention passes through initiator 2, and the use of 4-diamino-diphenyl amine then can obtain nano level polypyrrole particle.
Its reason mainly is that 4-diamino-diphenyl amine is more much lower than pyrroles's chemical oxidation current potential owing to 2, and in pyrroles's polymeric starting stage, the initiator of catalytic amount and pyrroles carry out copolymerization, quickens pyrroles's polymeric homogeneous nucleation speed, improves its chain growth speed.
In addition, because 2,4-diamino-diphenyl amine contains the diamine base, under acidic conditions, it can with form ammonium salt with hydrogen ion.Simultaneously, the pentanoic of the other end has hydrophobicity with respect to formed ammonium salt.This has caused ammonium salt and sour anionic hydrophilic end and pentanoic hydrophobic side self-assembly to form nano-microcapsule.In other words, 2,4-diamino-diphenyl amine can form the nano-microcapsule of self stabilization in acid solution, cause pyrroles and oxygenant to be formed nanometer ball by the embedding polymerization.Hence one can see that, and the size of self-assembly nano microcapsule depends on the volume size of the acid of using, i.e. small volume acid causes the polypyrrole nanometer ball of low dimensional, and vice versa.
Beneficial effect of the present invention
At first; A kind of controllable size polypyrrole nano particle of the present invention; Owing in the preparation process, do not add any emulsifying agent or template; Adopt different acid, oxygenant and initiator content to change behavior of pyrroles's chemical oxidising polymerisation and polypyrrole nano particle assembling mode, thereby the particle size of the polypyrrole nano particle of final gained is controlled.
Simultaneously, because these reaction conditionss can change the doping level and the oxidation state of polypyrrole, thereby realize controlledization to polypyrrole nano particle electric conductivity.。
And, because institute's synthetic polypyrrole nano particle can efficiently disperse in the preparation process, solve the unmanageable technical barrier of conductive polymers in water, alcohol and multiple organic solvent.
In addition, the preparation method of a kind of controllable size polypyrrole nano particle of the present invention is simple, efficient, and particulate diameter and electric conductivity height are controlled.
Description of drawings
Fig. 1, with 2 of 0%, 2% and 10% concentration, 4-diamino-diphenyl amine initiator, iron trichloride are oxidation
The synthetic polypyrrole particulate dynamic light shot of agent footpath distribution plan;
Fig. 2, with 2 of 0% concentration, 4-diamino-diphenyl amine is that initiator, iron trichloride are the synthetic pyrrole that gathers of oxygenant
Cough up the particulate scanning electron microscope diagram;
Fig. 3, with 2 of 10% concentration, 4-diamino-diphenyl amine is that to be that oxygenant is synthetic gather for initiator, iron trichloride
The scanning electron microscope diagram of pyrroles's nano particle;
Fig. 4, with concentration be 0%, 2% and 10% 2,4-diamino-diphenyl amine is that initiator, iron trichloride do
Synthetic polypyrrole nano particle of oxygenant and initiator 2,4-diamino-diphenyl amine self-polymerization gained
The particulate infrared absorpting light spectra;
Fig. 5, with 2% and 10% 2,4-diamino-diphenyl amine is that to be that oxygenant is synthetic gather for initiator, iron trichloride
Pyrroles's nano particle and initiator 2, the particulate ultraviolet of 4-diamino-diphenyl amine self-polymerization gained is inhaled
Receive spectrogram;
Fig. 6, with 2 of 10% concentration, 4-diamino-diphenyl amine is that to be that oxygenant is synthetic gather for initiator, ammonium persulphate
The scanning electron microscope diagram of pyrroles's nano particle;
Fig. 7, with 2 of 10% concentration, 4-diamino-diphenyl amine is that to be that oxygenant is synthetic gather for initiator, SRM 935a
The scanning electron microscope diagram of pyrroles's nano particle;
Fig. 8, with 2 of 10% concentration, 4-diamino-diphenyl amine is that initiator, iron trichloride are oxygenant, 1.0mol/L
The scanning electron microscope diagram of synthetic polypyrrole nano particle in the hydrochloric acid medium;
Fig. 9, with 2 of 10% concentration, 4-diamino-diphenyl amine is that initiator, iron trichloride are oxygenant, 1.0mol/L
The scanning electron microscope diagram of synthetic polypyrrole nano particle in the nitric acid medium;
Figure 10, with 2 of 10% concentration, 4-diamino-diphenyl amine be initiator, iron trichloride be oxygenant,
1.0mol/L the scanning electron microscope diagram of synthetic polypyrrole nano particle among the perchloric acid medium;
Figure 11, with 2 of 10% concentration, 4-diamino-diphenyl amine be initiator, iron trichloride be oxygenant,
1.0mol/L the scanning electron microscope diagram of synthetic polypyrrole nano particle in the camphorsulfonic acid medium.
Embodiment
Below through embodiment and combine accompanying drawing that the present invention is further set forth, but do not limit the present invention.
The apparent productive rate of a kind of controllable size polypyrrole nano particle of gained of the present invention calculates through formula (1):
Wherein, M
1Charging capacity (g) for pyrrole monomer;
M
2Be 2, the charging capacity (g) of 4-diamino-diphenyl amine initiator;
M
0Quality (g) for final gained polypyrrole.
The structure, form and the performance characterization method that the present invention relates to multipolymer are following:
Uv absorption spectrum characterizes
Adopt HP 8453 type uv absorption spectrum appearance, at room temperature the methyl alcohol dispersion liquid of the polypyrrole nano particle of about 0.001～0.005 g/L of concentration is tested.
Sem characterizes
Polypyrrole nano particle aqueous dispersions is directly dropped on the silicon chip, treat the sample seasoning after, adopt JEOL JSM 6700 type field emission scanning electron microscopes that its microscopic appearance is observed; Before observing sample all being carried out metal spraying (Pt) handles.
Conductivity test
Take by weighing the dry good polypyrrole powder of 50mg, utilize infrared tabletting machine that it is pressed into the sequin of certain thickness (d); Evenly coat two parallel elargol lines that length and spacing are 1cm in the identical faces of compressing tablet then; After treating the elargol drying, contact two bullion tree laces respectively with two probes, then through HP 3458A type two probe ohmmeters read its square resistance that records (
R Sq ); According to formula (2) electric conductivity of polypyrrole nano particle is calculated.
Wherein, parallel the carrying out 5 times of all specific conductivity tests averaged then.
The instrument that the present invention is used
Infrared absorption spectrometer, JASCO 420 class, Japanese beam split company;
The uv absorption spectrum appearance, HP 8453 types, hewlette-packard;
Ultimate analysis adopts Vario Macro CHN type elemental analyser to accomplish through combustion experiment by U.S. Columbia Analytical Services company.
Field emission scanning electron microscope, JEOL JSM 6700 types, Zhu Shi commercial firm of NEC;
Two probe ohmmeters, HP 3458A, hewlette-packard.
Pyrroles, 2,4-diamino-diphenyl amine, Youxiaolin, ydrogen peroxide 50, ammonium persulphate, SRM 935a, Anhydrous Ferric Chloride, dichloride are ferrous all available from German Sigma company;
Hydrochloric acid, nitric acid, perchloric acid, camphorsulfonic acid are all available from U.S. Fisher Scientific company.
Embodiment 1
A kind of preparation method of controllable size polypyrrole nano particle does not add initiator, and promptly initiator 2; The concentration of 4-diamino-diphenyl amine is 0%, is first solvent with methyl alcohol, is oxygenant with the FERRIC CHLORIDE ANHYDROUS; With pure water is second solvent, and its preparation method specifically may further comprise the steps:
(1), the 250mg pyrrole monomer is dissolved in 150mL alcohol and forms the pyrrole monomer alcoholic solution;
Wherein, described alcohol is methyl alcohol;
(2), the 600mg oxygenant is dissolved in the 150mL pure water formation aqueous oxidizing agent solution;
Described oxygenant is an iron trichloride;
(3), with the pyrrole monomer solution of step (1) gained and the aqueous oxidizing agent solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, the mol ratio of described pyrrole monomer and oxygenant is 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
The preparation method of a kind of controllable size polypyrrole of a kind of controllable size polypyrrole nano particle nano particle; Promptly with concentration be 2% 2; 4-diamino-diphenyl amine is initiator, is first solvent with methyl alcohol, is oxygenant with the FERRIC CHLORIDE ANHYDROUS; With pure water is second solvent, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 15mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in the 150mL alcoholic solution;
Wherein, described alcohol is methyl alcohol;
Wherein, described pyrrole monomer and initiator mol ratio are 49:1, and promptly initiator concentration is 2%;
(2), the 600mg oxygenant is dissolved in the 150mL pure water formation aqueous oxidizing agent solution;
Described oxygenant is an iron trichloride;
(3), blend solution that the pyrrole monomer of step (1) gained and initiator are formed and the aqueous oxidizing agent solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
Embodiment 3
The preparation method of a kind of controllable size polypyrrole of a kind of controllable size polypyrrole nano particle nano particle; Promptly with concentration be 10% 2; 4-diamino-diphenyl amine is initiator, is first solvent with methyl alcohol, is oxygenant with the FERRIC CHLORIDE ANHYDROUS; With pure water is second solvent, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in the 150mL alcoholic solution;
Wherein, described alcohol is methyl alcohol;
Wherein, described pyrrole monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 600mg oxygenant is dissolved in the 150mL pure water formation aqueous oxidizing agent solution;
Described oxygenant is a FERRIC CHLORIDE ANHYDROUS;
(3), with the pyrrole monomer solution of step (1) gained and the aqueous oxidizing agent solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
The above embodiments 1, embodiment 2 and embodiment 3 gained polypyrrole particulate dynamic light scattering analytical resultss are seen Fig. 1.As can be seen from Figure 1 in polyreaction, add and be merely 2% initiator; Prepared polypyrrole particle is reduced to nano-scale (380nm) by micron-scale (1.14 μ m), and its pattern has become the comparatively granular particles of the homogeneous of dispersive, nano-scale from the particle aggregate by micron-scale.Continuing increases initiator content to 10%, and the nano-scale of polymkeric substance is reduced to 282nm.Therefore show that the content of initiator has material impact to dispersiveness, microscopic dimensions and the pattern of polypyrrole.
Through sem Fig. 2 is seen in the observation of the polypyrrole product microscopic appearance of embodiment 1 gained.The result shows discovery, and it is oxygenant that embodiment 1 adopts iron trichloride, and the traditional method synthetic polypyrrole that does not add initiator presents the hundreds of nanometer to particle cluster polymers micron-scale, irregular.
Through sem the observations that embodiment 3 adds 10% concentration initiator synthetic polypyrrole product microscopic appearance is seen Fig. 3, as can be seen from Figure 3 the polypyrrole product particle of gained appears uniformly, size is about 300nm.The adding that shows initiator thus also has material impact to the productive rate that polymer nano granules forms.
Among the embodiment 1 when not adding initiator, 0
oThe apparent productive rate of synthetic polypyrrole is merely 2.7% under the C, and add among the embodiment 2 be merely 2% initiator after, the apparent productive rate of product is increased to 26.5% rapidly.Among the embodiment 3 when initiator content increases to 10%, the apparent productive rate of product and then increase to 42.6% fast.Continue to increase initiator content, the rising that then tends towards stability of the apparent productive rate of product explains that the adding of initiator largely improves pyrroles's polymerization velocity.
The above embodiments 1 do not add initiator, embodiment 2, and to add concentration be that to add concentration be that 10% initiator gained polypyrrole particle and initiator self adopt the infrared absorption spectrum analysis result of the product of iron trichloride oxypolymerization gained to see Fig. 4 for 2% initiator, embodiment 3.
As can be seen from Figure 4 behind the initiator self-polymerization, formed the oligopolymer with similar polyaniline structure, its infrared signature absorption peak is in 740cm respectively
-1, 1032cm
-1, 1480cm
-1And 1580cm
-1
After in pyrroles's polymerization system, adding the initiator of 2% and 10% concentration in addition, the product that obtains is closely similar with the diffuse reflectance infrared spectroscopy of the polypyrrole that does not add the initiator gained, promptly at 1472cm
-1And 1550cm
-1The place occur pyrrole ring the stretching vibration absorption peak (Mazur M. Preparation of surface-supported polypyrrole capsules using a solidified droplets template approach [J]. Journal of Physical Chemistry B; 2009,113 (3): 728-733.); At 1690cm
-1Stretching vibration peak (the Zhang W X of the pyrrole ring of partially oxidation appears in the place; Wen X G; Yang S H. Synthesis and characterization of uniform arrays of copper sulfide nanorods coated with nanolayers of polypyrrole [J]. Langmuir; 2003,19 (10): 4420-4426.); At 1032cm
-1And 1301cm
-1Stretching vibration peak (the Li X G of C-N appears in the place; Wei F; Huang M R; Xie Y B. Facile synthesis and intrinsic conductivity of novel pyrrole copolymer nanoparticles with inherent self-stability [J]. Journal of Physical Chemistry B, 2007,111 (21): 5829-5836.); At 923cm
-1And 1202cm
-1Intrinsic absorption peak (the Zhang X of doping attitude polypyrrole appears in the place; Zhang J; Song W; Liu Z F. Controllable synthesis of conducting polypyrrole nanostructures [J]. Journal of Physical Chemistry B, 2006,110 (3): 1158-1165.).
Above-mentioned data results shows, the polymkeric substance of pyrroles really of the product that initiated polymerization obtains.Ultimate analysis shows, is respectively 55.0/16.3/4.5 with the C/N/H weight ratio of the polypyrrole of the initiator content preparation of 10% concentration.C/N ratio through calculating this product is 3.38, this with the C/N of pure polypyrrole than (3.43) very near (Tran H D, Shin K; Hong W G, D'Arcy J M, Kojima RW; Weiller B H; Kaner R B. A template-free route to polypyrrole nanofibers [J]. Macromolecular Rapid Communications, 2007,28 (24): 2289-2293.).Polypyrrole product that it should be noted that initiated polymerization formation is at 740cm
-1A small acromion appears in the place, shows that pyrroles's polymkeric substance of formation contains a spot of initiator chain link.
Adding concentration with embodiment 2 is that to add concentration be 10% initiator for 2% initiator, embodiment 3; Iron trichloride is that oxygenant synthetic polypyrrole nano particle and initiator self adopt the uv absorption spectra of iron trichloride oxypolymerization products therefrom to see Fig. 5; It as can be seen from Figure 5 is oxygenant with the iron trichloride; The polypyrrole product for preparing under the different initiator content conditions mainly contains two absorption peaks at the methyl alcohol dispersion liquid, and promptly the position corresponds to π-π * transition of electron and n-π * dipole transition (Jang J in the polypyrrole respectively respectively at 300 – 380nm and 900nm place; Yoon H. Formation mechanism of conducting polypyrrole nanotubes in reverse micelle systems [J]. Langmuir; 2005,21 (24): 11484-11489.), see Fig. 5.And the initiator self-polymerization generates oligomer of phenylamine; π-π * the transition of electron and n-π * dipole transition (the Huang J X that occur similar polyaniline at 285nm and 585nm; Kaner R B. A general chemical route to polyaniline nanofibers [J]. Journal of American Chemistry Society; 2004,126 (3): 851-855.).Because the transition state of dipole can reflect the slight change of conjugated polymers molecular chain configuration, thereby can know the conjugated degree of polymkeric substance from the position at this peak.Along with the minimizing of initiator content, the chance that forms multipolymer with the pyrroles reduces, and resulting polymers is more near real polypyrrole.
Along with 2, the content of 4-diamino-diphenyl amine is increased at 100% o'clock by 0% respectively, and the specific conductivity of product reduces.Electric conductivity 3.5 * 10 by pure polypyrrole
-3S/cm reduces to<10
-10S/cm.The lasting reduction of specific conductivity is because 2 on the polypyrrole chain backbone, due to the existence of the rigidity phenylbenzene that 4-diamino-diphenyl amine chain link is contained.Pyrrole group in the pure polypyrrole of the space steric effect of phenylbenzene is many greatly, thereby the degree increase that causes the synthetic product polymer molecular chain to be distorted, and has reduced the coplanarity of molecular chain; Make the systematicness of piling up of polymer molecular chain descend simultaneously, make the polymer chain spacing increase.The conjugate length that this has just shortened conductive polymers widely makes that the plyability of electric transmission track reduces in the conjugated system, causes electronics at polymkeric substance interchain even many with the transmission difficulty in the chain.Therefore, the electric conductivity of the polypyrrole nano particle of adding initiator preparation descends many.
Embodiment 4
The preparation method of a kind of controllable size polypyrrole of a kind of controllable size polypyrrole nano particle nano particle; Promptly with concentration be 10% 2; 4-diamino-diphenyl amine is initiator, is first solvent with methyl alcohol, is oxygenant with the ammonium persulphate; With pure water is second solvent, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in 150mL alcohol;
Wherein, described alcohol is methyl alcohol;
Wherein, described monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 845mg oxygenant is dissolved in the pure water of 150mL the formation aqueous oxidizing agent solution;
Described oxygenant is an ammonium persulphate;
(3), with the pyrrole monomer solution of step (1) gained and the aqueous oxidizing agent solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
Embodiment 5
A kind of preparation method of controllable size polypyrrole nano particle, promptly with concentration be 10% 2,4-diamino-diphenyl amine is initiator; With methyl alcohol is first solvent; With the SRM 935a is oxygenant, is second solvent with pure water, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in 150mL alcohol;
Wherein, described alcohol is methyl alcohol;
Wherein, described monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 1088mg oxygenant is dissolved in the pure water of 150mL the formation aqueous oxidizing agent solution;
Described oxygenant is a SRM 935a;
(3), with the pyrrole monomer solution of step (1) gained and the aqueous oxidizing agent solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
Embodiment 6
A kind of preparation method of controllable size polypyrrole nano particle, promptly with concentration be 10% 2,4-diamino-diphenyl amine is initiator; With methyl alcohol is first solvent; Hypochlorous sodium is an oxygenant, is second solvent with pure water, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in 150mL alcohol;
Wherein, described alcohol is methyl alcohol;
Wherein, described monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 275mg oxygenant is dissolved in the pure water of 150mL the formation aqueous oxidizing agent solution;
Described oxygenant is a Youxiaolin;
(3), with the pyrrole monomer solution of step (1) gained and the aqueous oxidizing agent solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution of step (3) gained is taken out back control rotating speed is 4500r/min, the time is 30min centrifugal settling, can not get solid product.
Embodiment 7
A kind of preparation method of controllable size polypyrrole nano particle, promptly with concentration be 10% 2,4-diamino-diphenyl amine is initiator; With methyl alcohol is first solvent; Ydrogen peroxide 50 is an oxygenant in proper order, is second solvent with pure water, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in 150mL alcohol;
Wherein, described alcohol is methyl alcohol;
Wherein, described monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 150mg oxygenant is dissolved in the pure water of 150mL the formation aqueous oxidizing agent solution;
Described oxygenant is a ydrogen peroxide 50;
(3), with the pyrrole monomer solution of step (1) gained and the aqueous oxidizing agent solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution of step (3) gained is taken out back control rotating speed is 4500r/min, the time is 30min centrifugal settling, can not get solid product.
Can find out that from embodiment 3,4,5,6 and embodiment 7 redox potential of different oxygenants has marked difference, influence chemical oxidising polymerisation speed, thereby cause the chainpropagation of polypyrrole different.Different oxygenant kinds have material impact like Youxiaolin, ydrogen peroxide 50, SRM 935a, ammonium persulphate and iron trichloride etc. to polypyrrole is synthetic.
Can find out that from embodiment 6 and embodiment 7 Youxiaolin that oxidation capacity is more weak and ydrogen peroxide 50 can not oxidation pyrroles polymerizations, finally can not get the polypyrrole nano-particle product.
And embodiment 5 with the SRM 935a be oxygenant under the situation that does not have acid, oxidation capacity also a little less than, the apparent productive rate that the polypyrrole nano particle is formed is 11.1%.
Embodiment 4 is that oxygenant and embodiment 3 are that oxygenant then is easy to make the pyrroles to carry out polymerization with the iron trichloride with the ammonium persulphate, forms black polypyrrole nano particle, and the apparent productive rate of its product is respectively 73.5% and 42.6%.
The electron scanning micrograph of the foregoing description 3, embodiment 4 and embodiment 5 synthetic polypyrrole nano particles is seen Fig. 3, Fig. 6 and Fig. 7 respectively.Sem observation finds, adopting iron trichloride, ammonium persulphate and SRM 935a is that the size of the polymer beads that obtains of oxygenant is respectively 200 250nm, 300 500nm and 90 200nm.And adopt oxidation capacity more weak oxygenant such as SRM 935a relatively, the nano grain surface that obtains is more smooth and more be tending towards forming the particulate state body, and vice versa.
Along with the raising increase of oxygenant oxidation current potential, polypyrrole nano particle team electric conductivity progressively increases.
Embodiment 3,4,5 is respectively with 2 of 10% concentration, and 4-diamino-diphenyl amine is initiator, and adopting iron trichloride, ammonium persulphate and SRM 935a respectively is oxygenant, and the specific conductivity of the product that obtains under the same terms is respectively 3.7 * 10
-5S/cm, 4.0 * 10
-6S/cm with<10
-10S/cm.This possibly be that pyrrole monomer can be fully oxidized in strong well-oxygenated environment, and the conjugate length of the chain structure of the polymkeric substance that obtains improves, and makes electronics between polymer chain, form effectively transmission more easily, thereby has improved the specific conductivity of product.
Embodiment 8
A kind of preparation method of controllable size polypyrrole nano particle, promptly with 2 of 10% concentration, 4-diamino-diphenyl amine is initiator, be first solvent with methyl alcohol; With the iron trichloride is oxygenant; With 1.0mol/L hydrochloric acid is second solvent, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in 150mL alcohol;
Wherein, described alcohol is methyl alcohol;
Wherein, described monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 600mg oxygenant is dissolved in the 150ml acid solution, formation oxygenant acid solution;
Described acid is the hydrochloric acid of 1.0 mol/L;
Described oxygenant is a FERRIC CHLORIDE ANHYDROUS;
(3), with the pyrrole monomer solution of step (1) gained and the oxygenant acid solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
Embodiment 9
A kind of preparation method of controllable size polypyrrole nano particle, promptly with 2 of 10% concentration, 4-diamino-diphenyl amine is initiator, be first solvent with methyl alcohol; With the iron trichloride is oxygenant; With 1.0mol/L nitric acid is second solvent, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in 150mL alcohol;
Wherein, described alcohol is methyl alcohol;
Wherein, described monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 600mg oxygenant is dissolved in the 150ml acid solution, formation oxygenant acid solution;
Described acid is the nitric acid of 1.0 mol/L;
Described oxygenant is a FERRIC CHLORIDE ANHYDROUS;
(3), with the pyrrole monomer solution of step (1) gained and the oxygenant acid solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
A kind of preparation method of controllable size polypyrrole nano particle, promptly with 2 of 10% concentration, 4-diamino-diphenyl amine is initiator, be first solvent with methyl alcohol; With the iron trichloride is oxygenant; With 1.0mol/L perchloric acid is second solvent, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in 150mL alcohol;
Wherein, described alcohol is methyl alcohol;
Wherein, described monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 600mg oxygenant is dissolved in the 150ml acid solution, formation oxygenant acid solution;
Described acid is the perchloric acid of 1.0 mol/L;
Described oxygenant is a FERRIC CHLORIDE ANHYDROUS;
(3), with the pyrrole monomer solution of step (1) gained and the oxygenant acid solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
Embodiment 11
A kind of preparation method of controllable size polypyrrole nano particle, promptly with 2 of 10% concentration, 4-diamino-diphenyl amine is initiator, be first solvent with methyl alcohol; With the iron trichloride is oxygenant; With the 1.0mol/L camphorsulfonic acid is second solvent, and its preparation method specifically may further comprise the steps:
(1), with 250mg pyrrole monomer and 75mg initiator 2,4-diamino-diphenyl amine solvent forms monomer and initiator blend solution in 150mL alcohol;
Wherein, described alcohol is methyl alcohol;
Wherein, described monomer and initiator mol ratio are 9:1, and promptly initiator concentration is 10%;
(2), the 600mg oxygenant is dissolved in the 150ml acid solution, formation oxygenant acid solution;
Described acid is the camphorsulfonic acid of 1.0 mol/L;
Described oxygenant is a FERRIC CHLORIDE ANHYDROUS;
(3), with the pyrrole monomer solution of step (1) gained and the oxygenant acid solution of step (2) gained, be cooled to 0
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
Wherein, described pyrrole monomer and oxygenant mol ratio are 1:1;
(4), the reaction solution taking-up back control rotating speed with step (3) gained is 4500r/min; Time obtains solid product for 30min centrifugal settling, and be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the formed mixed solvent of 9:1 washs above-mentioned gained;
Repeat above-mentioned centrifugal settling again, wash 3～5 times, after centrifugal again, with the flush away oligopolymer, have neither part nor lot in initiator and the remaining oxygenant etc. of reaction on a small quantity, then 50
oC down control vacuum tightness is under the condition of 0.09MPa after dry 7 days, obtains black polypyrrole nano particle.
Generally, mineral acid in pyrroles's polymerization process and phenanthrene be essential.But mineral acid provides proton when polymerization, and 2, this aminated compounds of 4-diamino-diphenyl amine exists under the situation, the electric charge of reaction system is issued have material impact, thereby is changed dispersiveness, size and the pattern of institute's synthetic polymer particle.
Sem shows that the median size of the polypyrrole nano particle of the foregoing description 8, embodiment 9, embodiment 10 and embodiment 11 gained is respectively 85nm, 93nm, 188nm and 282nm, sees Fig. 8, Fig. 9, Figure 10 and Figure 11 respectively.
Adopt the specific conductivity of different acid medium synthetic polypyrrole nano particles also different.The specific conductivity of the foregoing description 8, embodiment 9, embodiment 10 and the embodiment 11 synthetic polypyrrole nano particles that obtain is respectively 3.0 * 10
-5S/cm, 7.2 * 10
-5S/cm, 1.4 * 10
-5S/cm and 4.0 * 10
-6S/cm.This possibly be because, pyrroles, oxygenant and the initiator different solubility in different acid solutions, the product that causes obtaining has formed different molecular chain structures.Nitric acid not only has very strong acidity because of it and also has certain oxidisability, thereby causes the electric conductivity of product the highest.The acid of differing mol diameter can change the doping attitude of product, the also specific conductivity of impact polymer.
Above-mentioned specific embodiment just is used for the present invention that explains, rather than limits the invention, and in spirit of the present invention and claim protection domain, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (3)
1. the preparation method of a controllable size polypyrrole nano particle is characterized in that pyrrole monomer and initiator are dissolved in first kind of solvent formation pyrrole monomer and initiator blend solution;
Oxygenant is dissolved in second kind of solvent forms oxidizing agent solution;
Again with initiator solution and pyrrole monomer blend solution with acutely rock after oxidizing agent solution mixes moments later standing and reacting fully after, carry out centrifugal, washing, drying etc., finally obtain controllable size polypyrrole nano particle;
Wherein, described initiator is 2,4-diamino-diphenyl amine;
Described first kind of solvent is methyl alcohol, ethanol or Virahol;
Described oxygenant is that Youxiaolin, ydrogen peroxide 50, ammonium persulphate, SRM 935a, FERRIC CHLORIDE ANHYDROUS or ydrogen peroxide 50/dichloride are ferrous;
Described second solvent is that water or concentration are hydrochloric acid, nitric acid, perchloric acid or the camphorsulfonic acid of 1.0mol/L;
Described pyrrole monomer and initiator 2, the mol ratio of 4-diamino-diphenyl amine is 9～49:1;
Described pyrrole monomer and oxygenant mol ratio are 0.2～2:1.
2. the preparation method of a kind of controllable size polypyrrole nano particle as claimed in claim 1 is characterized in that specifically may further comprise the steps:
(1), with pyrrole monomer and 2,4-diamino-diphenyl amine solvent forms pyrrole monomer and initiator blend solution in first kind of solvent;
(2), oxygenant is dissolved in second kind of solvent, the formation oxidizing agent solution;
(3), the pyrrole monomer of step (1) gained and the oxidizing agent solution of initiator blend solution and step (2) gained are cooled to 0 respectively
oC, short mix is acutely rocked about 10s with mixed solution then, and placing response 24h obtains reaction solution after reacting completely then;
(4), the reaction solution of step (3) gained is taken out back control rotating speed is 4500r/min, the time obtains solid product for 30min centrifugal settling;
Be water by volume with 3 times water and methyl alcohol again: methyl alcohol is the solid product that the mixing solutions of formed water of 9:1 and methyl alcohol washs above-mentioned gained;
Repeat the centrifugal again supernatant that goes after the above-mentioned centrifugal settling, washing step 3～5 times, then 50 ℃ down the control vacuum tightnesss be dry under the condition of 0.02～0.09MPa, promptly get the polypyrrole nano particle.
3. according to claim 1 or claim 2 a kind of the gathering of preparing method's gained of controllable size polypyrrole nano particle
Pyrroles's nano particle is characterized in that polypyrrole nano particle diameter is 80～600nm, and electric conductivity does
10
-2～10
-7S/cm。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102766250A (en) * | 2012-07-31 | 2012-11-07 | 中国科学院宁波材料技术与工程研究所 | Polythiophene microballs and preparation method thereof |
| CN104387957A (en) * | 2014-11-13 | 2015-03-04 | 山东华亚环保科技有限公司 | Antistatic coating and preparation method thereof |
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| CN104624068A (en) * | 2015-01-22 | 2015-05-20 | 天津大学 | Method for polypyrrole nano material modified polymer ultrafiltration membrane |
| CN109251326A (en) * | 2018-08-17 | 2019-01-22 | 西南交通大学 | The preparation method of the good conducting high polymers object nano particle of aqueous phase dispersibility |
| CN110146564A (en) * | 2019-05-06 | 2019-08-20 | 湘潭大学 | It is a kind of that hydrotalcite/organic polymer composite material H is carried based on silver2O2Without enzyme sensor preparation method |
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2011
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| YAOZU LIAO ET.AL.: "Facile synthesis of water-dispersible conducting polymer nanospheres", 《ACS NANO》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102766250A (en) * | 2012-07-31 | 2012-11-07 | 中国科学院宁波材料技术与工程研究所 | Polythiophene microballs and preparation method thereof |
| CN102766250B (en) * | 2012-07-31 | 2015-01-28 | 中国科学院宁波材料技术与工程研究所 | Polythiophene microballs and preparation method thereof |
| CN104387957A (en) * | 2014-11-13 | 2015-03-04 | 山东华亚环保科技有限公司 | Antistatic coating and preparation method thereof |
| CN104624068A (en) * | 2015-01-22 | 2015-05-20 | 天津大学 | Method for polypyrrole nano material modified polymer ultrafiltration membrane |
| CN104530427A (en) * | 2015-01-27 | 2015-04-22 | 齐鲁工业大学 | Preparation method of solid aristate spherical conducting copolymer |
| CN109251326A (en) * | 2018-08-17 | 2019-01-22 | 西南交通大学 | The preparation method of the good conducting high polymers object nano particle of aqueous phase dispersibility |
| CN109251326B (en) * | 2018-08-17 | 2021-04-09 | 西南交通大学 | Preparation method of conductive high-molecular polymer nanoparticles with good water phase dispersibility |
| CN110146564A (en) * | 2019-05-06 | 2019-08-20 | 湘潭大学 | It is a kind of that hydrotalcite/organic polymer composite material H is carried based on silver2O2Without enzyme sensor preparation method |
| CN110229330A (en) * | 2019-06-27 | 2019-09-13 | 东北大学 | A kind of environmentally protective synthetic method and its application of polypyrrole |
| WO2020258383A1 (en) * | 2019-06-27 | 2020-12-30 | 东北大学 | Green and environmentally-friendly synthesis method and application of polypyrrole |
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