CN105504278B - A kind of method for synthesizing polypyrrole - Google Patents
A kind of method for synthesizing polypyrrole Download PDFInfo
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- CN105504278B CN105504278B CN201610115327.2A CN201610115327A CN105504278B CN 105504278 B CN105504278 B CN 105504278B CN 201610115327 A CN201610115327 A CN 201610115327A CN 105504278 B CN105504278 B CN 105504278B
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- polypyrrole
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- sodium sulfate
- polyethylene glycol
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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 present invention relates to a kind of method for synthesizing polypyrrole, this method is that lauryl sodium sulfate, polyethylene glycol 2000, ethanol, butanol, Peracetic acid, pyrrole monomer are mixed and be sufficiently stirred for, then by ultrasound, washing, drying to obtain polypyrrole product.Method of the present invention to be different from traditional synthesis polypyrrole, using Peracetic acid as strong oxidizer and the polypyrrole that there is highly acid to prepare.The polypyrrole that the present invention is prepared has the advantages that purity is high, is easily isolated, production capacity is high, reaction condition is gentle, environment-friendly, stability is high.
Description
Technical field
The invention belongs to the technical field that chemical oxidization method synthesizes polypyrrole, the present invention is in biology, chemical industry, material, super
The technical fields such as capacitor, anti-corrosion of metal are widely used.
Background technology
In recent years, due to the high speed development of China's economic, various energy and material resource problems are also increasingly in short supply, macromolecule material
The synthesis of material, which gives people to live, brings earth-shaking change, and high polymer material is to anti-corrosion of metal, electrode material, biological field
Deng certain change is all brought, the energy of country has both been saved, the waste of resource is turn avoid.The synthesis of high polymer material is
Focus as people's growing interest, a few days ago in the research of high polymer material, polypyrrole has been acknowledged as most potential
One of high polymer material.There are some researches show protection of the polypyrrole film to metal serves shielding and passivation, polypyrrole
Also there is higher conductance, stability is good in the environment, is a kind of electrode material of preferable polymer secondary battery, poly- pyrrole
Coughing up also has unique doping performance, can carry out a certain degree of modification to polypyrrole, obtained in terms of electro-catalysis very well
Application, polypyrrole also have good Bc, so equally also having obtained large-scale application in biological field.For
Polypyrrole high polymer is obtained, people study and attempted various methods (referring to chemical oxidization method synthesis at this)；
(1) ammonium persulfate method；Ammonium persulfate is added in deionized water, and mechanical agitation 1h makes ammonium persulfate fully dissolve,
Acetic acid or hydrochloric acid conditioning solution pH=3 or so is added dropwise, can also add a small amount of dispersant, fast drop through refrigeration pyrrole monomer (or
Person's ice bath), mechanical agitation 4-6h pulls atrament out, ultrasound, washs three times, 50 DEG C of vacuum drying 24h, you can obtain product.
Because ammonium persulfate is water miscible, polypyrrole prepared by this method can only be prepared in aqueous phase solvent, in oil phase solvent, over cure
Sour ammonium is insoluble, can be wrapped among polypyrrole, and obtained polypyrrole purity is low.
(2) tri-chlorination iron processes；Ferric trichloride, mechanical agitation 1h are added in deionized water so that liquor ferri trichloridi energy
Enough fully dissolvings, it is same that acetic acid or hydrochloric acid conditioning solution pH=3 or so is added dropwise, a small amount of dispersant is added dropwise, fast drop is through cold
The pyrrole monomer (or ice bath) of Tibetan, mechanical agitation 4-6h pulls atrament out, ultrasound, washs three times, 50 DEG C of vacuum drying
24h, you can obtain product.Disturbed because ferric trichloride is soluble in water with strong color, be unfavorable for color in polypyrrole synthesis
The observation of change, and have the doping of iron ion among synthesis polypyrrole, the purity to polypyrrole has a certain impact.
(3) hydrogen peroxide method；Excessive hydrogenperoxide steam generator is added dropwise in deionized water, mechanical agitation causes hydrogen peroxide
It is fully dispersed in the solution to come, nitrogen can be led to before monomer is added dropwise and does protection gas, hydrochloric acid or acetic acid, which is added dropwise, makes solution
PH=3 or so, fast drop pyrrole monomer untill mechanical agitation black polypyrrole generation to be had, pulls atrament out, ultrasound,
Washing three times, 50 DEG C of vacuum drying 24h, you can obtain product.Time-consuming for the polypyrrole of this method synthesis, and stability is poor, yield
It is low.
Above-mentioned three kinds of methods can be transferred through oxidizing process synthesis polypyrrole, but all be the water-soluble inorganic salt in aqueous phase solvent
Peracetic acid is organic peroxide in synthesis, the present invention, can also can be among interface in aqueous phase solvent, in oil phase solvent
Effectively synthesize polypyrrole.Polypyrrole high polymer is easy to polymerize by pyrrole monomer, there is strong oxygen under strongly acidic conditions
Agent exists or can prepare polypyrrole high polymer with the presence of high potential difference.The polypyrrole of chemical oxidization method synthesis is big
It is mostly powdered, and the polypyrrole of electrochemical method synthesis is mostly film-form, to chemical oxidization method composite powder in the present invention
The method of the polypyrrole of last shape carries out a certain degree of innovation.Pyrroles is slightly soluble in water, but in acid condition, pyrrole monomer
Dissolubility is very big.It is main in the present invention to provide acidity to add Peracetic acid as strong oxidizer and Peracetic acid for reaction solution
Environment, polypyrrole high polymer can be prepared by the Peracetic acid for adding various concentrations.PH is little on synthesis polypyrrole influence,
Under strongly acidic conditions can.The polypyrrole that the invention is prepared has that purity is high, be easily isolated, production capacity is high, reaction condition
Gently, it is environment-friendly, the advantages of stability is high, energy resource consumption is also saved to a certain extent.
The content of the invention
It is an object of the invention to propose that one kind newly has polypyrrole synthetic method.
Polypyrrole synthetic method of the present invention, by lauryl sodium sulfate, polyethylene glycol 2000, ethanol, butanol, mistake
Fluoroacetic acid, pyrrole monomer are mixed and are sufficiently stirred for, then by ultrasound, washing, drying to obtain polypyrrole product.
Wherein, the mass percent of each composition is：0.2-0.35% lauryl sodium sulfate, 0.3-0.4% polyethylene glycol
2000,0.1-0.2% ethanol, 0.5-0.6% butanol, 4-10% Peracetic acid, 2.5-3% pyrrole monomers, remaining is deionization
Water, altogether 100%.
Wherein, consumption preferably is：Lauryl sodium sulfate percentage is 0.2%, and the percentage of polyethylene glycol 2000 is
0.35%, the percentage of ethanol is 0.1%, and the percentage of butanol is 0.5%, and the percentage of Peracetic acid is 10%, Bi Kadan
The percentage of body is 3%, and remaining is deionized water, altogether 100%.
Comprise the following steps that；
(1) lauryl sodium sulfate and polyethylene glycol 2000 are added in deionized water, at ambient temperature (or ice bath,
Ice bath is better), mechanical agitation so that lauryl sodium sulfate and polyethylene glycol 2000 dissolving are complete；
(2) ethanol, butanol solution are added dropwise in above-mentioned solution, adds Peracetic acid and continues mechanical agitation, keep solution
PH=3, because Peracetic acid is strong acid, being added dropwise can also make solution be in highly acid on a small quantity.
(3) in above-mentioned solution, fast drop pyrrole monomer continues mechanical agitation, atrament life has been stirred to always
As only, atrament is pulled out, ultrasound is washed 4-6 times with absolute ethyl alcohol, 50 DEG C of vacuum drying, you can obtain product.By what is obtained
Product is ground, you can obtain polypyrrole body of powder, the polypyrrole particle after grinding is uniform, it is easy to characterizes, is also easy to commercial Application.
After fast drop pyrrole monomer, in the presence of having oxidant in system, in a polypyrrole monomer point of electroneutral
Son can be oxidized in the presence of oxidant and lose an electronics, become radical cation, latter two right radical cation
Collision is combined into the polypyrrole of dication two containing two radical cations in system, and dication now is in system
Middle process disproportionation generates two polypyrroles in electroneutral.Two polypyrroles of electroneutral again can be with the cation in system
Free radical, which be combined with each other, generates the radical cation of three polypyrroles, the polypyrrole of tripolymer is generated by disproportionation, week
And the polypyrrole for having ultimately generated long chain is renewed,
It is due to that pyrrole monomer is unstable that pyrrole monomer is refrigerated to (3 DEG C) in advance, meets light heat chance oxidant easy
React, while the pyrrole monomer after refrigeration is conducive to the polymerization of pyrrole monomer.Lauryl sodium sulfate is added with gathering
Ethylene glycol 2000 does compound surfactant, mainly improves the dispersive property of polypyrrole, and S elements can be doped into pyrroles
Monomer, can carry out a certain degree of modification (can find out from power spectrum and X-ray polycrystalline diffraction) to polypyrrole, add ethanol master
If playing a part of froth breaking, the addition of ethanol in addition also promotes the polymerization of pyrrole monomer to a certain extent, adds butanol master
If playing a part of cosurfactant.
Described pyrrole monomer is all that, by deepfreeze, temperature is 3 DEG C, and described Peracetic acid is all that content is
40%, described deionized water is all laboratory self-control deionized water.
The innovative point of the present invention is, with conventional method ratio；
(1) have substantial degradation first in energy efficiency consumption, Peracetic acid is both strong oxidizer and strong acid, therefore
Unnecessary acid need not be added dropwise can provide sour environment, more safety and environmental protection to reaction solution, and 40% Peracetic acid has acid
Property it is strong, it is low to human injury because Peracetic acid can make disinfectant among daily life, and hydrochloric acid, high volatility, corrosion
Property it is strong, and have a certain degree of harm to human body.
(2) purity is higher, and particle is uniform, the almost introducing without impurity, and color change is obvious, observation that can be apparent
The change of color when polymerizeing to pyrrole monomer.
(3) the maximum innovation of the present invention is that either in aqueous phase solvent, in oil phase solvent, or among interface
Polypyrrole can be synthesized.And there is the polypyrrole prepared product to be easily isolated, production capacity high, reaction condition is gentle, environment-friendly,
Stability is high, low cost and other advantages, the synthesis of polypyrrole powder for being that a kind of technique is simple, preparation process is easy to operate and controlling
Method.
Polypyrrole is no crystalline structure in itself, but because adding a small amount of lauryl sodium sulfate, has part ion to be doped to
Among polypyrrole, so by XRD (X-ray diffraction) it can be seen that appearance, is synthesized when without lauryl sodium sulfate
During polypyrrole, XRD occurs without peak.
Brief description of the drawings
The high polymer TEM figures for the polypyrrole that the Peracetic acid of Fig. 1 a 10% is prepared.
The high polymer TEM figures for the polypyrrole that the Peracetic acid of Fig. 1 b 4% is prepared.
The polypyrrole high polymer infrared spectrum that Fig. 2 is prepared.
Embodiment
With reference to specific embodiment, the present invention will be described in detail, it is necessary to explanation, protection scope of the present invention
It is not limited in following embodiments.
Explanation：Medicine used in the present invention is commercially available prod or laboratory conventional medication.
The preparation of reaction solution；Deionized water 40ml, 0.2g lauryl sodium sulfate, 0.35g polyethylene glycol 2000s, on a small quantity
Butanol, ethanol, plus 10ml Peracetic acid, pH=3.
The processing of reaction monomers；Lucifuge, Cord blood, separate with strong acid, highly basic, strong oxidizer.
The preparation of Peracetic acid；The content for preparing Peracetic acid is 40%.
The content of Peracetic acid is added dropwise by changing, changes mixed emulsifier content to synthesis polypyrrole without influence, only
Have an impact in terms of dispersiveness, keep other conditions constant, experiment is compared, so as to draw optimum proportioning.
Experimental method；
The present invention observes table using Tecnai12 transmission electron microscopes, Fourier infrared spectrograph, Powder X-ray Diffractometer
Levy the pattern of the polypyrrole of preparation.From figure 2, it is seen that 797cm-1The flexural vibrations of the c h bond of the wide absworption peak correspondence polypyrrole in place,
1556cm-1The peak correspondence polypyrrole N-H vibration absorption peaks at place, 1182cm-1The stretching vibration of correspondence C-N keys, 3194cm-1Correspondence
Polypyrrole N-H stretching vibrations.Although preparing the external environment of polypyrrole difference, its result can equally be prepared poly-
Pyrroles's high polymer.
Embodiment 1：
0.2% lauryl sodium sulfate, 0.35% polyethylene glycol 2000,0.1% ethanol, 0.5% butanol, 10% peroxide second
Acid, 3% pyrrole monomer, remaining is deionized water (amounting to 100%), continues mechanical agitation, keeps the pH=3 of solution, soon
Pyrrole monomer is added dropwise in speed, and continuing mechanical agitation 24h has a large amount of atraments to generate, and pulls atrament out, and ultrasound uses absolute ethyl alcohol
Wash 4-6 times, 50 DEG C of vacuum drying 24h, you can obtain product, obtained product is ground, you can obtain polypyrrole body of powder.
Embodiment 2：
0.25% lauryl sodium sulfate, 0.30% polyethylene glycol 2000,0.2% ethanol, 0.55% butanol, 8% peroxide
Acetic acid, 3% pyrrole monomer, remaining is deionized water (amounting to 100%), continues mechanical agitation, keeps the pH=3 of solution,
Fast drop pyrrole monomer, continuing mechanical agitation 30h has more atrament to generate, and pulls atrament out, and ultrasound uses anhydrous second
Alcohol is washed 4-6 times, 50 DEG C of vacuum drying 24h, you can obtain product, obtained product is ground, you can obtain polypyrrole body of powder.
Embodiment 3：
0.35% lauryl sodium sulfate, 0.40% polyethylene glycol 2000,0.15% ethanol, 0.60% butanol, 6% peroxide
Acetic acid, 3% pyrrole monomer, remaining is deionized water (amounting to 100%), continues mechanical agitation, keeps the pH=3 of solution,
Fast drop pyrrole monomer, continuing mechanical agitation 36h has atrament generation, pulls atrament out, and ultrasound is washed with absolute ethyl alcohol
4-6 times, 50 DEG C of vacuum drying 24h, you can obtain product, obtained product is ground, you can obtain polypyrrole body of powder.
Embodiment 4：
0.20% lauryl sodium sulfate, 0.35% polyethylene glycol 2000,0.1% ethanol, 0.50% butanol, 4% peroxide
Acetic acid, 2.5% pyrrole monomer, remaining is deionized water (amounting to 100%), continues mechanical agitation, the pH=3 for keeping solution is
Can, fast drop pyrrole monomer, continuing mechanical agitation 48h has a small amount of atrament to be generated as pulling atrament out, ultrasound, with nothing
Water-ethanol is washed 4-6 times, 50 DEG C of vacuum drying 24h, you can obtain product, obtained product is ground, you can obtain polypyrrole powder
Opisthosoma.
Experimental result is determined as；Drawn a conclusion by embodiment 1,2,3,4 with Fig. 1 a, 1b, using Peracetic acid as Strong oxdiative
The polypyrrole of agent synthesis, in the case where keeping other conditions constant, within the specific limits, the amount of oxidant is more, and monomer is got over
Many, the time required for reaction is shorter, and yield is also higher.
Claims (3)
1. a kind of method for synthesizing polypyrrole, it is characterised in that by lauryl sodium sulfate, polyethylene glycol 2000, ethanol, fourth
Alcohol, Peracetic acid, pyrrole monomer are mixed and are sufficiently stirred for, then by ultrasound, washing, drying to obtain polypyrrole product；Reaction
In system, by mass percentage, consumption is each composition：0.2-0.35% lauryl sodium sulfate, 0.3-0.4% polyethylene glycol
2000,0.1-0.2% ethanol, 0.5-0.6% butanol, 4-10% Peracetic acid, 2.5-3% pyrrole monomers, remaining is deionization
Water.
2. the method for polypyrrole is synthesized according to claim 1, it is characterised in that comprised the following steps that；
(1) lauryl sodium sulfate and polyethylene glycol 2000 are added in deionized water；Mechanical agitation makes lauryl sodium sulfate
It is complete with polyethylene glycol 2000 dissolving；
(2) ethanol, butanol solution are added dropwise in above-mentioned solution, adds Peracetic acid and continues mechanical agitation, keep the pH=of solution
3,
(3) in above-mentioned solution, fast drop pyrrole monomer continues mechanical agitation, atrament has been stirred to always and has been generated as
Only, atrament is pulled out, ultrasound is washed 4-6 times with absolute ethyl alcohol, 50 DEG C of vacuum drying obtain product.
3. the method for polypyrrole is synthesized according to claim 1, it is characterised in that the percentage of lauryl sodium sulfate is
0.2%, the percentage of polyethylene glycol 2000 is 0.35%, and the percentage of ethanol is 0.1%, and the percentage of butanol is 0.5%, mistake
The percentage of fluoroacetic acid is 10%, and the percentage of pyrrole monomer is 3%, and remaining is deionized water, altogether 100%.
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| CN108097069A (en) * | 2017-11-24 | 2018-06-01 | 浙江工业大学 | A kind of method that polypyrrole Monovalent selectivity cation-exchange membrane is prepared in situ |
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| 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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| 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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| CN108097069A (en) * | 2017-11-24 | 2018-06-01 | 浙江工业大学 | A kind of method that polypyrrole Monovalent selectivity cation-exchange membrane is prepared in situ |
| 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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