CN105504278A - Method for synthesizing polypyrrole - Google Patents
Method for synthesizing polypyrrole Download PDFInfo
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- CN105504278A CN105504278A CN201610115327.2A CN201610115327A CN105504278A CN 105504278 A CN105504278 A CN 105504278A CN 201610115327 A CN201610115327 A CN 201610115327A CN 105504278 A CN105504278 A CN 105504278A
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- polypyrrole
- peracetic acid
- macrogol
- sodium lauryl
- pyrrole monomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
Abstract
The invention relates to a method for synthesizing polypyrrole. The method includes mixing lauryl sodium sulfate, polyethylene glycol 2000, ethyl alcohol, butanol, peracetic acid and pyrrole monomers with one another to obtain mixtures and sufficiently stirring the mixtures; carrying out ultrasonic treatment on the mixtures and washing and drying the mixtures to obtain polypyrrole products. The method is different from the traditional method for preparing polypyrrole, the peracetic acid is used as a strong oxidizer and is strong in acidity, and accordingly the polypyrrole can be prepared by the aid of the method. The method has the advantages that the polypyrrole prepared by the aid of the method is high in purity, capacity and stability and is environmental friendly, separation can be facilitated, reaction conditions are mild, and the like.
Description
Technical field
The invention belongs to the technical field of chemical oxidization method synthesis polypyrrole, the present invention is widely used in technical fields such as biology, chemical industry, material, ultracapacitor, anti-corrosion of metal.
Background technology
In recent years, due to the high speed development of China's economic, various energy and material resource problem is also day by day in short supply, the synthesis of macromolecular material brings earth-shaking change to people's life, macromolecular material all brings certain change to anti-corrosion of metal, electrode materials, biological field etc., both save the national energy, turn avoid the waste of resource.The synthesis of macromolecular material has become the focus of people's growing interest, and a few days ago in the research of macromolecular material, polypyrrole has been acknowledged as one of macromolecular material of most potentiality.There are some researches show; the protection of polypyrrole film to metal serves shielding and passivation; polypyrrole also has higher electric conductivity; good stability is in the environment a kind of electrode materials of desirable polymer secondary battery, and polypyrrole also has unique doping performance; the modification can carrying out to a certain degree to polypyrrole; in electrocatalysis, obtain good application, polypyrrole also has good Bc, so have also been obtained large-scale application equally at biological field.In order to obtain polypyrrole superpolymer, people study and have attempted various way (this place refers to that chemical oxidization method synthesizes);
(1) ammonium persulphate method; Add ammonium persulphate in deionized water, mechanical stirring 1h, makes ammonium persulphate fully dissolve, and drips acetic acid or hydrochloric acid conditioning solution about pH=3, also a small amount of dispersion agent can be added, fast drop is through the pyrrole monomer (or ice bath) of refrigeration, and mechanical stirring 4-6h, pulls atrament out, ultrasonic, wash three times, 50 DEG C of vacuum-drying 24h, can obtain product.Because ammonium persulphate is water miscible, polypyrrole prepared by the method can only be prepared in aqueous phase solvent, and in oil phase solvent, ammonium persulphate is insoluble, can be wrapped in the middle of polypyrrole, and the polypyrrole purity obtained is low.
(2) tri-chlorination iron processes; Add iron trichloride in deionized water, mechanical stirring 1h, makes liquor ferri trichloridi fully to dissolve, same dropping acetic acid or hydrochloric acid conditioning solution about pH=3, drip a small amount of dispersion agent, fast drop is through the pyrrole monomer (or ice bath) of refrigeration, and mechanical stirring 4-6h, pulls atrament out, ultrasonic, wash three times, 50 DEG C of vacuum-drying 24h, can obtain product.Because iron trichloride is soluble in water, there is strong color interference, be unfavorable for the observation of colour-change in polypyrrole synthesis, and have the doping of iron ion in the middle of synthesis polypyrrole, the purity of polypyrrole is had a certain impact.
(3) hydrogen peroxide method; Drip excessive superoxol in deionized water; mechanical stirring makes hydrogen peroxide fully spread out in the solution; nitrogen can be led to and do protection gas before dropping monomer, about dropping hydrochloric acid or acetic acid make pH value of solution=3, fast drop pyrrole monomer; till mechanical stirring black polypyrrole to be had generates; pull atrament out, ultrasonic, wash three times; 50 DEG C of vacuum-drying 24h, can obtain product.The polypyrrole length consuming time of the method synthesis, poor stability, yields poorly.
Above-mentioned three kinds of methods can synthesize polypyrrole by oxidation style, but be all water-soluble inorganic salt synthesis in aqueous phase solvent, in the present invention, Peracetic Acid is organo-peroxide, also in the middle of interface, effectively can synthesize polypyrrole in aqueous phase solvent, in oil phase solvent.Polypyrrole superpolymer, easily via pyrrole monomer polymerization, has strong oxidizer to exist under strongly acidic conditions or has high potential difference to exist and can both prepare polypyrrole superpolymer.The polypyrrole of chemical oxidization method synthesis is mostly Powdered, and the polypyrrole of electrochemical method synthesis is mostly film like, to the innovation carried out with the method for the polypyrrole of chemical oxidization method composite powder powder to a certain degree in the present invention.Pyrroles is slightly soluble in water, but in acid condition, the solvability of pyrrole monomer is very large.Mainly to add Peracetic Acid for strong oxidizer and Peracetic Acid provides sour environment for reaction soln in the present invention, polypyrrole superpolymer can be prepared by the Peracetic Acid of interpolation different concns.PH is little on the impact of synthesis polypyrrole, under strongly acidic conditions can.The polypyrrole that this invention is prepared have purity high, be easy to be separated, production capacity is high, reaction conditions is gentle, environmental friendliness, stability advantages of higher, also saves energy consumption to a certain extent.
Summary of the invention
The object of the invention is to propose one and newly have polypyrrole synthetic method.
Polypyrrole synthetic method of the present invention, by sodium lauryl sulphate, Macrogol 2000, ethanol, butanols, Peracetic Acid, pyrrole monomer mixing fully stirring, then through ultrasonic, wash, be drying to obtain polypyrrole product.
Wherein, the mass percent of each composition is: 0.2-0.35% sodium lauryl sulphate, 0.3-0.4% Macrogol 2000,0.1-0.2% ethanol, 0.5-0.6% butanols, 4-10% Peracetic Acid, 2.5-3% pyrrole monomer, and all the other are deionized water, amounts to 100%.
Wherein, preferred consumption is: sodium lauryl sulphate percentage ratio is 0.2%, the percentage ratio of Macrogol 2000 is 0.35%, the percentage ratio of ethanol is 0.1%, the percentage ratio of butanols is 0.5%, and the percentage ratio of Peracetic Acid is 10%, and the percentage ratio of pyrrole monomer is 3%, all the other are deionized water, amount to 100%.
Concrete steps are as follows;
(1) sodium lauryl sulphate and Macrogol 2000 are added in deionized water, at ambient temperature (or ice bath, ice bath effect better), mechanical stirring, make sodium lauryl sulphate and Macrogol 2000 dissolve completely;
(2) in above-mentioned solution, drip ethanol, butanol solution, add Peracetic Acid and continue mechanical stirring, keep the pH=3 of solution, because Peracetic Acid is strong acid, drip and solution also can be made to be strongly-acid on a small quantity.
(3) in above-mentioned solution, fast drop pyrrole monomer, continues mechanical stirring, and till being stirred to atrament generation, pull atrament out, ultrasonic, wash 4-6 time with dehydrated alcohol, 50 DEG C of vacuum-dryings, can obtain product always.By the product grinding obtained, polypyrrole body of powder can be obtained, the polypyrrole uniform particles after grinding, be easy to characterize, be also easy to industrial application.
After fast drop pyrrole monomer, when there being oxygenant to exist in system, oxidizedly under the effect of oxygenant an electronics can be lost in an electroneutral polypyrrole monomer molecule, become radical cation, so latter two radical cation collides dication two polypyrrole be combined into containing two radical cations in system, and dication now generates one in electroneutral two polypyrroles through disproportionation in system.Electroneutral two polypyrroles can be combined with each other with the radical cation in system again the radical cation of generation three polypyrrole, generate trimerical polypyrrole, go round and begin again and finally generate the polypyrrole of long molecular chain through disproportionation,
Being carried out in advance by pyrrole monomer refrigerating (3 DEG C) is because pyrrole monomer is unstable, and meet light heat chance oxygenant and easily react, the pyrrole monomer simultaneously after refrigeration is conducive to the polymerization of pyrrole monomer.Add sodium lauryl sulphate and Macrogol 2000 does compound surfactant, mainly improve the dispersing property of polypyrrole, and S element can be doped into pyrrole monomer, the modification (can find out from power spectrum and X-ray polycrystalline diffraction) can carrying out to a certain degree to polypyrrole, add the effect that ethanol mainly plays froth breaking, in addition ethanol add the polymerization also facilitating pyrrole monomer to a certain extent, add the effect that butanols mainly plays cosurfactant.
Described pyrrole monomer is all through deepfreeze, and temperature is 3 DEG C, and described Peracetic Acid is all content is 40%, and described deionized water is all laboratory self-control deionized water.
Innovative point of the present invention is, with traditional method ratio;
(1) first have substantial degradation in energy efficiency consumption, Peracetic Acid is strong oxidizer is also strong acid, therefore can provide sour environment to reaction soln, safety and environmental protection more without the need to dripping unnecessary acid, the Peracetic Acid of 40% has acid strong, low to human injury, because Peracetic Acid can make sterilizing agent in the middle of daily life, and hydrochloric acid, high volatility, corrodibility is strong, and has harm to a certain degree to human body.
(2) purity is higher, uniform particles, does not almost have the introducing of impurity, and colour-change is obvious, clearly can observe the change of color during pyrrole monomer polymerization.
(3) innovation that the present invention is maximum is just no matter be in aqueous phase solvent, in oil phase solvent, or can synthesize polypyrrole in the middle of interface.And the polypyrrole prepared has that product is easy to be separated, production capacity is high, reaction conditions is gentle, environmental friendliness, stability are high, low cost and other advantages, be that a kind of technique is simple, the synthetic method of the polypyrrole powder of preparation process convenient operation and control.
Polypyrrole itself is without crystalline structure, but because adding a small amount of sodium lauryl sulphate, have part ion to be doped in the middle of polypyrrole, so can see peak by XRD (X-ray diffraction), during the polypyrrole synthesized when not adding sodium lauryl sulphate, XRD occurs without peak.
Accompanying drawing explanation
The superpolymer TEM of the polypyrrole that Fig. 1 a10% Peracetic Acid is prepared schemes.
The superpolymer TEM of the polypyrrole that Fig. 1 b4% Peracetic Acid is prepared schemes.
The polypyrrole superpolymer infrared spectrum that Fig. 2 prepares.
Embodiment
Describe the present invention below in conjunction with specific embodiment, it should be noted that, protection scope of the present invention is not limited in following embodiment.
Illustrate: the medicine used in the present invention is commercially available prod or laboratory conventional medication.
The preparation of reaction soln; Deionized water 40ml, 0.2g sodium lauryl sulphate, 0.35g Macrogol 2000, a small amount of butanols, ethanol, add 10ml Peracetic Acid, pH=3.
The process of reaction monomers; Lucifuge, cryopreservation, to separate with strong acid, highly basic, strong oxidizer.
The preparation of Peracetic Acid; The content of preparation Peracetic Acid is 40%.
By changing the content dripping Peracetic Acid, changing mixed emulsifier content to synthesizing polypyrrole without impact, only in dispersed, having impact, keeping other conditions constant, compare test, thus draw optimum proportioning.
Experimental technique;
The present invention adopts Tecnai12 transmission electron microscope, Fourier infrared spectrograph, Powder X-ray Diffractometer to observe the pattern of the polypyrrole characterizing preparation.As can be seen from Figure 2,797cm
-1locate the flexural vibration of the c h bond of the corresponding polypyrrole of wide absorption peak, 1556cm
-1the peak corresponding polypyrrole N-H vibration absorption peak at place, 1182cm
-1the stretching vibration of corresponding C-N key, 3194cm
-1corresponding polypyrrole N-H stretching vibration.Although prepare the external environment difference to some extent of polypyrrole, its result can prepare polypyrrole superpolymer equally.
Embodiment 1:
0.2% sodium lauryl sulphate, 0.35% Macrogol 2000,0.1% ethanol, 0.5% butanols, 10% Peracetic Acid, 3% pyrrole monomer, all the other are deionized water (amounting to 100%), continue mechanical stirring, keep the pH=3 of solution, fast drop pyrrole monomer, continuing mechanical stirring 24h has a large amount of atrament to generate, pull atrament out, ultrasonic, wash 4-6 time with dehydrated alcohol, 50 DEG C of vacuum-drying 24h, can product be obtained, by the product grinding obtained, polypyrrole body of powder can be obtained.
Embodiment 2:
0.25% sodium lauryl sulphate, 0.30% Macrogol 2000,0.2% ethanol, 0.55% butanols, 8% Peracetic Acid, 3% pyrrole monomer, all the other are deionized water (amounting to 100%), continue mechanical stirring, keep the pH=3 of solution, fast drop pyrrole monomer, continuing mechanical stirring 30h has more atrament to generate, pull atrament out, ultrasonic, wash 4-6 time with dehydrated alcohol, 50 DEG C of vacuum-drying 24h, can product be obtained, by the product grinding obtained, polypyrrole body of powder can be obtained.
Embodiment 3:
0.35% sodium lauryl sulphate, 0.40% Macrogol 2000,0.15% ethanol, 0.60% butanols, 6% Peracetic Acid, 3% pyrrole monomer, all the other are deionized water (amounting to 100%), continue mechanical stirring, keep the pH=3 of solution, fast drop pyrrole monomer, continuing mechanical stirring 36h has atrament to generate, pull atrament out, ultrasonic, wash 4-6 time with dehydrated alcohol, 50 DEG C of vacuum-drying 24h, can product be obtained, by the product grinding obtained, polypyrrole body of powder can be obtained.
Embodiment 4:
0.20% sodium lauryl sulphate, 0.35% Macrogol 2000,0.1% ethanol, 0.50% butanols, 4% Peracetic Acid, 2.5% pyrrole monomer, all the other are deionized water (amounting to 100%), continue mechanical stirring, keep the pH=3 of solution, fast drop pyrrole monomer, continuation mechanical stirring 48h has a small amount of atrament to be generated as to pull atrament out, ultrasonic, wash 4-6 time with dehydrated alcohol, 50 DEG C of vacuum-drying 24h, can obtain product, by the product grinding obtained, polypyrrole body of powder can be obtained.
Experimental result is determined as; Being reached a conclusion by embodiment 1,2,3,4 and Fig. 1 a, 1b, take Peracetic Acid as the polypyrrole of strong oxidizer synthesis, when keeping other conditions constant, within the specific limits, the amount of oxygenant is more, and monomer is more, time required for reaction is shorter, and output is also higher.
Claims (4)
1. synthesize a method for polypyrrole, it is characterized in that, by sodium lauryl sulphate, Macrogol 2000, ethanol, butanols, Peracetic Acid, pyrrole monomer mixing fully stirring, then through ultrasonic, wash, be drying to obtain polypyrrole product.
2. synthesize the method for polypyrrole according to claim 1, it is characterized in that, concrete steps are as follows;
(1) sodium lauryl sulphate and Macrogol 2000 are added in deionized water; Mechanical stirring makes sodium lauryl sulphate and Macrogol 2000 dissolve completely;
(2) in above-mentioned solution, drip ethanol, butanol solution, add Peracetic Acid and continue mechanical stirring, keep the pH=3 of solution,
(3) in above-mentioned solution, fast drop pyrrole monomer, continues mechanical stirring, and till being stirred to atrament generation, pull atrament out, ultrasonic, wash 4-6 time with dehydrated alcohol, 50 DEG C of vacuum-dryings, namely obtain product always.
3. synthesize the method for polypyrrole according to claim 1, it is characterized in that, in reaction system, by mass percentage, consumption is each composition: 0.2-0.35% sodium lauryl sulphate, 0.3-0.4% Macrogol 2000,0.1-0.2% ethanol, 0.5-0.6% butanols, 4-10% Peracetic Acid, 2.5-3% pyrrole monomer, all the other are deionized water.
4. synthesize the method for polypyrrole according to claim 3, it is characterized in that, the percentage ratio of sodium lauryl sulphate is 0.2%, the percentage ratio of Macrogol 2000 is 0.35%, and the percentage ratio of ethanol is 0.1%, and the percentage ratio of butanols is 0.5%, the percentage ratio of Peracetic Acid is 10%, the percentage ratio of pyrrole monomer is 3%, and all the other are deionized water, amounts to 100%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108565040A (en) * | 2018-05-04 | 2018-09-21 | 芜湖天科生物科技有限公司 | A kind of whisker type battery conductive material and preparation method thereof |
| CN111495427A (en) * | 2020-05-28 | 2020-08-07 | 陕西科技大学 | Full-organic conjugated polymer photocatalytic material and preparation method thereof |
| CN112751033A (en) * | 2020-12-30 | 2021-05-04 | 远景动力技术(江苏)有限公司 | Polar solvent-resistant lithium supplement additive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108097069B (en) * | 2017-11-24 | 2021-05-11 | 浙江工业大学 | Method for in-situ preparation of polypyrrole monovalent selective cation exchange membrane |
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| CN1432033A (en) * | 2000-04-04 | 2003-07-23 | 潘尼珀尔有限公司 | Method and appts. for preparing polyaniline |
| CN102051048A (en) * | 2010-11-10 | 2011-05-11 | 西北师范大学 | Polypyrrole/graphene nano composite and preparation method thereof |
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- 2016-03-01 CN CN201610115327.2A patent/CN105504278B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432033A (en) * | 2000-04-04 | 2003-07-23 | 潘尼珀尔有限公司 | Method and appts. for preparing polyaniline |
| CN102051048A (en) * | 2010-11-10 | 2011-05-11 | 西北师范大学 | Polypyrrole/graphene nano composite and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108565040A (en) * | 2018-05-04 | 2018-09-21 | 芜湖天科生物科技有限公司 | A kind of whisker type battery conductive material and preparation method thereof |
| CN111495427A (en) * | 2020-05-28 | 2020-08-07 | 陕西科技大学 | Full-organic conjugated polymer photocatalytic material and preparation method thereof |
| CN112751033A (en) * | 2020-12-30 | 2021-05-04 | 远景动力技术(江苏)有限公司 | Polar solvent-resistant lithium supplement additive and preparation method thereof |
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