CN105330855A - Polyaniline and preparation method thereof - Google Patents
Polyaniline and preparation method thereof Download PDFInfo
- Publication number
- CN105330855A CN105330855A CN201410322605.2A CN201410322605A CN105330855A CN 105330855 A CN105330855 A CN 105330855A CN 201410322605 A CN201410322605 A CN 201410322605A CN 105330855 A CN105330855 A CN 105330855A
- Authority
- CN
- China
- Prior art keywords
- solution
- polyaniline
- iron plate
- preparation
- precooling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a polyaniline and a preparation method thereof. The method includes the following steps: mixing an aqueous solution of inorganic acid with an oxidizer to obtain a first solution; mixing the aqueous solution of inorganic acid with aniline monomer to obtain a second solution; adjusting the first solution and the second solution to a reaction temperature for precooling; maintaining the reaction temperature, slowly adding the precooled first solution into the precooled second solution, and standing for 0.5-3 h to obtain a polyaniline paste. The polyaniline prepared by the method exists in a paste form in aqueous phase, has good dispersion and machinability, and can be widely used in the technical field of anti-corrosion; at the same time, the preparation process is simple, and low in cost.
Description
Technical field
The present invention relates to phenyl amines polymkeric substance, particularly relate to a kind of polyaniline and preparation method thereof.
Background technology
In numerous macromolecular material, polyaniline due to raw material cheap, the advantages such as synthesis technique is simple, and physical and chemical stability is good, and the high and electrochromism of specific conductivity is good, become the focus that recent domestic is studied.
The polyreaction of polyaniline is a very complicated process, temperature of reaction, oxidant species and consumption, and the acidity of reaction system all can cause very large impact to this reaction, and the performance difference such as structure, the polymerization degree of the polyaniline finally obtained is very big.
In traditional preparation technology, what the preparation method of polyaniline of the overwhelming majority finally obtained is all pulverous polyaniline precipitation.Because polyaniline is indissoluble thing, bad dispersibility in a solvent, therefore, workability is poor.At present, relatively more conventional method is that doping uses macromolecular organic acid in the polyaniline molecule of eigenstate, as sulphosalicylic acid and the Witco 1298 Soft Acid etc. of adulterating, thus improve polyaniline solubleness in a solvent, and then improve polyaniline solubleness in a solvent and film-forming properties.But this kind of technique is not only loaded down with trivial details, and considerably increase production cost because organic acid uses.
Summary of the invention
The invention provides a kind of polyaniline and preparation method thereof, its method technique is simple, and preparation cost is cheap, and the polyaniline obtained has good dispersiveness in aqueous phase.
A preparation method for polyaniline, comprises the following steps:
Obtain solution: mixed with oxygenant by inorganic acid aqueous solution, obtains the first solution; Inorganic acid aqueous solution is mixed with aniline monomer, obtains the second solution;
Precooling: described first solution and described second solution are adjusted to temperature of reaction respectively and carry out precooling;
Reaction: keep temperature of reaction, slowly joined by the first solution after described precooling in the second solution after described precooling, obtains paste polyaniline after leaving standstill 0.5h ~ 3h.
Wherein in an embodiment, described temperature of reaction is 0 DEG C ~ 10 DEG C.
Wherein in an embodiment, the mol ratio of the aniline monomer in the oxygenant in described first solution and described second solution is (1 ~ 10): 1.
Wherein in an embodiment, in described first solution, the mol ratio of described mineral acid and described oxygenant is 1:(5 ~ 15).
Wherein in an embodiment, in described second solution, the mol ratio of described mineral acid and described aniline monomer is (5 ~ 15): 1.
Wherein in an embodiment, before described precooling step, further comprising the steps of:
Regulate pH value to 1 ~ 4 of described first solution and described second solution respectively.
Wherein in an embodiment, described aniline monomer is the mixture of aniline or aniline and anils;
Described anils is one or more in methyl o-aminobenzoate, anthranilic acid, adjacent pentanoic, adjacent cyano-aniline, o-toluidine and Ortho-Chloro aniline.
Wherein in an embodiment, described mineral acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and boric acid.
Wherein in an embodiment, described oxygenant is one or more in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
A kind of polyaniline, described polyaniline adopts the preparation method of above-mentioned polyaniline to be prepared from; Described polyaniline exists with cream form in aqueous phase.
Beneficial effect of the present invention is as follows:
Under oxygenant and aniline monomer are placed in acidic conditions by the preparation method of polyaniline of the present invention respectively, the pH value in reaction process is more easily controlled; And the mode that the present invention adopts first precooling to react again, in lower temperature range, molecular motion severe degree reduces, after polyreaction starts, carry out under the environment that polyreaction is wrapped up at solvent molecule, make polymerisate also be in the state of being wrapped up by solvent, exist with cream form in aqueous phase, not easily generate precipitation, there is dispersed and workability preferably; Meanwhile, the method preparation process is simple, with low cost.
Polyaniline provided by the invention exists with cream form in aqueous phase, has dispersed and workability preferably, is widely used in anticorrosion technique field.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of the preparation method of polyaniline of the present invention;
Fig. 2 is the reaction process schematic diagram utilizing the preparation method of polyaniline of the present invention to prepare an embodiment of polyaniline;
Fig. 3 is the infrared absorpting light spectra of the pasty polymer obtained in the embodiment of the present invention 1;
Fig. 4 is the gel permeation chromatography figure of the pasty polymer obtained in the embodiment of the present invention 1.
Embodiment
The present invention is described in detail below in conjunction with embodiment.It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.
The invention provides a kind of preparation method of polyaniline, prepare polymkeric substance by oxidizing aniline monomer.The method synthesis technique is simple, with low cost, is suitable for a large amount of production.
Composition graphs 1, the preparation method of polyaniline of the present invention comprises the following steps:
S100, obtain solution: mixed with oxygenant by inorganic acid aqueous solution, obtains the first solution; Inorganic acid aqueous solution is mixed with aniline monomer, obtains the second solution.
Under oxygenant and aniline monomer are placed in acidic conditions by this step respectively, the pH value in reaction process is more easily controlled.
First solution and the second solution pH value be less than 7.Hydrogen ion can improve the polymerization rate of aniline monomer, and can improve transformation efficiency, and within the specific limits, acidity is stronger, and the speed of response of aniline monomer is faster, and transformation efficiency is higher.Preferably, the pH value of the first solution and the second solution is 1 ~ 4, and with this understanding, aniline monomer has more high reaction rate and transformation efficiency.
As a kind of embodiment, in the first solution, the mol ratio of mineral acid and oxygenant is 1:(5 ~ 15).Wherein, mineral acid be preferably in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and boric acid one or more, it has stronger acidity, has lower price simultaneously, reduces preparation cost.Oxygenant is preferably the one or how several in ammonium persulphate, Potassium Persulphate and Sodium Persulfate, and it has stronger oxidation capacity, can improve the transformation efficiency of aniline monomer.
In second solution, the Main Function of mineral acid for dissolving aniline monomer, and provides sour environment.Because aniline monomer is organism, be insoluble in water, mineral acid can react with aniline, generates water-soluble salt, and dispersion in aqueous, makes oxidising process fully to react.
Preferably, in the second solution, the mol ratio of mineral acid and aniline monomer is (5 ~ 15): 1, makes aniline monomer fully can generate water-soluble salt, provides a sour environment simultaneously.Mineral acid be preferably in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and boric acid one or more.
In second solution, aniline monomer can be aniline, also can be the mixture of aniline and anils.As preferably, anils is one or more in methyl o-aminobenzoate, anthranilic acid, adjacent pentanoic, adjacent cyano-aniline, o-toluidine and Ortho-Chloro aniline.
In second solution, the add-on of aniline monomer can regulate according to the add-on of oxygenant in the first solution, and the consumption of oxygenant is too small, can affect the productive rate of polyaniline; The consumption of oxygenant is too large, then may cause the degraded of polyaniline.As preferably, the mol ratio of the aniline monomer in the oxygenant in the first solution and the second solution is (1 ~ 10): 1.
S200: the first solution and the second solution are adjusted to temperature of reaction respectively and carry out precooling.
The motion intense degree of solvent molecule in the first solution and the second solution can be reduced by precooling, be beneficial in subsequent step and obtain paste polyaniline.As a kind of embodiment, Pre-cooling Mode is water-bath or ice bath.
It should be noted that, temperature of reaction herein refers to that aniline monomer generates the temperature of polyaniline under the effect of oxygenant.
Wherein in an embodiment, before precooling step S200, further comprising the steps of: pH value to 1 ~ 4 regulating the first solution and the second solution respectively.If the pH value of the first solution prepared in S100 and the second solution is in the scope of 1 ~ 4, then without the need to regulating.
S300: keep temperature of reaction, slowly joined by the first solution after precooling in the second solution after precooling, obtains paste polyaniline after leaving standstill 0.5h ~ 3h.
Slow dropping in this step refers to and to drip with the speed of 1 ~ 3 per second; Paste polyaniline refers to that polyaniline exists with dense suspension liquid state in mixing solutions.
Preferably, as a kind of embodiment, temperature of reaction is preferably 0 DEG C ~ 10 DEG C.Polymerization under cold condition can make polymerisate be disperseed fully in the solution, not easily reunites or precipitation.This is due to before starting the reaction, and monomer is in the solution dispersed after dissolving, and is surrounded by solvent molecule; In lower temperature range, molecular motion severe degree reduces, after polyreaction starts, carry out under the environment that polyreaction is wrapped up at solvent molecule, polymerisate is also in by solvent package status, thus is disperseed in the solution, and not easily generate aggregate or precipitation.As shown in Figure 2, the reaction process schematic diagram for utilizing the preparation method of polyaniline of the present invention to prepare an embodiment of polyaniline.
The preparation method of polyaniline of the present invention, first adopts mineral acid by oxygenant and aniline monomer acidifying respectively, then is carried out precooling, be finally mixed to get polyaniline.By polyaniline prepared by this method, exist with cream form in aqueous phase, there is good dispersiveness, thus there is good workability; Meanwhile, the method preparation process is simple, and easily realize, preparation cost is cheap.
Present invention also offers a kind of polyaniline, utilize the preparation method of above-mentioned polyaniline to be prepared from.Polyaniline of the present invention exists with cream form in aqueous phase, has dispersed and workability preferably, is widely used in anticorrosion technique field.
In order to understand the present invention better, below by specific embodiment, the preparation method to polyaniline of the present invention further illustrates:
Embodiment 1
(1) hydrochloric acid soln of preparation containing 1 molar part HCl, adds 10 molar part ammonium persulphates, obtains the first solution that pH value is 1 after stirring in this hydrochloric acid soln;
(2) hydrochloric acid soln of preparation containing 150 molar part HCl, adds 8 molar part aniline and 2 molar part methyl o-aminobenzoates, obtains the second solution that pH value is 1 after stirring in this hydrochloric acid soln;
(3) water-bath the first solution and the second solution being placed in respectively 2 DEG C leaves standstill precooling;
(4) keep the temperature of 2 DEG C, the first solution after precooling is slowly joined in the second solution after precooling, leave standstill and obtain paste polymerisate after 1 hour.
See Fig. 3, it is the infrared absorpting light spectra of the paste polymerisate that the present embodiment obtains.Wherein, wave number is 3349cm
-1with 3218cm
-1two peaks at place are the stretching vibration peak of Amino End Group hydrogen; Wave number is 1401cm
-1the double bond that the absorption peak at place can be attributed to phenyl ring and quinone ring is stretched peak; Wave number is 1700cm
-1~ 1760cm
-1the superposing of absorption peak of carbonyl on to be phenyl ring with the double bond of quinone ring stretch the peak at place peak and ester group; Wave number is 1138cm simultaneously
-1place is C-O-C stretching vibration absorption peak.Drawn in product, to there is Amino End Group, conjugate ring and ester group by infrared spectra map analysis.
See Fig. 4, be gel permeation chromatography (GelPermeationChromatography, the GPC) figure of the paste polymerisate that the present embodiment obtains.As seen from the figure, the gel permeation chromatography of this pasty polymer is single-peak structure, and the number-average molecular weight that simultaneously can record product is 7351.
The test data of comprehensive infrared spectra and gel permeation chromatography, can obtain drawing a conclusion: the paste polymerisate that the present embodiment obtains is the polyaniline of macromolecular structure.
The polyaniline obtained the present embodiment below does Corrosion Protection test, and test process is as follows:
Get an iron plate, the polyaniline obtained by the present embodiment is applied to after mixing with epoxy resin, isophorone diamine on this iron plate; Iron plate after smearing is placed in vacuum drying oven and heats 3h, obtain the first coating iron plate.Separately get an identical iron plate, at the mixture of this iron plate surface smear epoxy resin and isophorone diamine, be then placed in vacuum drying oven and heat 3h, obtain the second coating iron plate.
It should be noted that, the coat-thickness of the first coating iron plate is equal with the coat-thickness of the second coating iron plate.
Above-mentioned first coating iron plate and the second coating iron plate are done salt-fog test.At 5wt.%NaCl, pH value is under the salt fog of solution formation of 6.5 ~ 7.2, temperature maintains 35 ± 1.7 DEG C, scratching is done to the coatingsurface of the first coating iron plate and the second coating iron plate, continuous exposure experiment 240h, can find that the degree that weathers of the second coating iron plate is far above the first coating iron plate.It can thus be appreciated that the polyaniline that the present embodiment obtains has excellent Corrosion Protection.
Embodiment 2
(1) preparation is containing 10 molar part H
2sO
4sulphuric acid soln, in this sulphuric acid soln, add 50 molar part ammonium persulphates, after stirring, obtain the first solution, regulate the pH of the first solution to be 4;
(2) preparation is containing 50 molar part H
2sO
4sulphuric acid soln, in this sulphuric acid soln, add 10 molar part aniline, after stirring, obtain the second solution, regulate the pH value of the second solution to be 4;
(3) ice bath the first solution and the second solution being placed in respectively 0 DEG C leaves standstill precooling;
(4) keep the temperature of 0 DEG C, the first solution after precooling is slowly joined in the second solution after precooling, leave standstill and obtain paste polymerisate after 3 hours.
Measure infrared spectra and the gel permeation chromatography of the paste polymerisate that the present embodiment obtains, result shows, the paste polymerisate obtained in the present embodiment is the polyaniline of macromolecular structure.
The polyaniline obtained the present embodiment below does Corrosion Protection test, and test process is as follows:
Get an iron plate, be applied to after the polyaniline of the present embodiment is mixed with epoxy resin and isophorone diamine on this iron plate; Iron plate after smearing is placed in vacuum drying oven and heats 3h, obtain the first coating iron plate.Separately get an identical iron plate, at the mixture of this iron plate surface smear epoxy resin and isophorone diamine, be then placed in vacuum drying oven and heat 3h, obtain the second coating iron plate.
It should be noted that, the coat-thickness of the first coating iron plate is equal with the coat-thickness of the second coating iron plate.
Above-mentioned first coating iron plate and the second coating iron plate are done salt-fog test.At 5wt.%NaCl, pH value is under the salt fog of solution formation of 6.5 ~ 7.2, temperature maintains 35 ± 1.7 DEG C, scratching is done to the coatingsurface of the first coating iron plate and the second coating iron plate, continuous exposure experiment 240h, can find that the degree that weathers of the second coating iron plate is far above the first coating iron plate.It can thus be appreciated that the polyaniline that the present embodiment obtains has excellent Corrosion Protection.
Embodiment 3
(1) preparation is containing 1 molar part HNO
3with the mixing solutions of 1 molar part HCl, in this mixing solutions, add 30 molar part ammonium persulphates, after stirring, obtain the first solution, regulate the pH value to 2 of the first solution;
(2) preparation is containing 20 molar part HNO
3with the mixing solutions of 10 molar part HCl, in this mixing solutions, add 3 molar part aniline, after stirring, obtain the second solution, regulate the pH value to 2 of the second solution;
(3) water-bath the first solution and the second solution being placed in respectively 2 DEG C leaves standstill precooling;
(4) keep the temperature of 2 DEG C, the first solution after precooling is slowly joined in the second solution after precooling, leave standstill and obtain paste polymerisate after 0.5 hour.
Measure infrared spectra and the gel permeation chromatography of the paste polymerisate that the present embodiment obtains, result shows, the paste polymerisate obtained in the present embodiment is the polyaniline of macromolecular structure.
The polyaniline obtained the present embodiment below does Corrosion Protection test, and test process is as follows:
Get an iron plate, be applied to after the polyaniline of the present embodiment is mixed with epoxy resin and isophorone diamine on this iron plate; Iron plate after smearing is placed in vacuum drying oven and heats 3h, obtain the first coating iron plate.Separately get an identical iron plate, at the mixture of this iron plate surface smear epoxy resin and isophorone diamine, be then placed in vacuum drying oven and heat 3h, obtain the second coating iron plate.
It should be noted that, the coat-thickness of the first coating iron plate is equal with the coat-thickness of the second coating iron plate.
Above-mentioned first coating iron plate and the second coating iron plate are done salt-fog test.At 5wt.%NaCl, pH value is under the salt fog of solution formation of 6.5 ~ 7.2, temperature maintains 35 ± 1.7 DEG C, scratching is done to the coatingsurface of the first coating iron plate and the second coating iron plate, continuous exposure experiment 240h, can find that the degree that weathers of the second coating iron plate is far above the first coating iron plate.It can thus be appreciated that the polyaniline that the present embodiment obtains has excellent Corrosion Protection.
Embodiment 4
(1) hydrochloric acid soln of preparation containing 1 molar part HCl, adds 5 molar part Sodium Persulfates and 2 molar part ammonium persulphates, obtains the first solution that pH value is 3 after stirring in this hydrochloric acid soln;
(2) hydrochloric acid soln of preparation containing 30 molar part HCl, adds 5 molar part aniline, obtains the second solution that pH value is 3 after stirring in this hydrochloric acid soln;
(3) water-bath that the first solution and step the second solution are placed in 2 DEG C is respectively left standstill precooling;
(4) keep the temperature of 2 DEG C, the first solution after precooling is slowly joined in the second solution after precooling, leave standstill and obtain paste polymerisate after 1 hour.
Measure infrared spectra and the gel permeation chromatography of the paste polymerisate that the present embodiment obtains, result shows, the paste polymerisate obtained in the present embodiment is the polyaniline of macromolecular structure.
The polyaniline obtained the present embodiment below does Corrosion Protection test, and test process is as follows:
Get an iron plate, be applied to after the polyaniline of the present embodiment is mixed with epoxy resin and isophorone diamine on this iron plate; Iron plate after smearing is placed in vacuum drying oven and heats 3h, obtain the first coating iron plate.Separately get an identical iron plate, at the mixture of this iron plate surface smear epoxy resin and isophorone diamine, be then placed in vacuum drying oven and heat 3h, obtain the second coating iron plate.
It should be noted that, the coat-thickness of the first coating iron plate is equal with the coat-thickness of the second coating iron plate.
Above-mentioned first coating iron plate and the second coating iron plate are done salt-fog test.At 5wt.%NaCl, pH value is under the salt fog of solution formation of 6.5 ~ 7.2, temperature maintains 35 ± 1.7 DEG C, scratching is done to the coatingsurface of the first coating iron plate and the second coating iron plate, continuous exposure experiment 240h, can find that the degree that weathers of the second coating iron plate is far above the first coating iron plate.It can thus be appreciated that the polyaniline that the present embodiment obtains has excellent Corrosion Protection.
Embodiment 5
(1) hydrochloric acid soln of preparation containing 1 molar part HCl, adds 10 molar part Potassium Persulphates, obtains the first solution after stirring, regulate the pH of the first solution to be 4 in this hydrochloric acid soln;
(2) hydrochloric acid soln of preparation containing 40 molar part HCl, adds 5 molar part aniline, obtains the second solution after stirring, regulate the pH of the first solution to be 2 in this hydrochloric acid soln;
(3) water-bath the first solution and the second solution being placed in respectively 10 DEG C leaves standstill precooling;
(4) keep the temperature of 10 DEG C, the first solution after precooling is slowly joined in the second solution after precooling, leave standstill and obtain paste polymerisate after 1 hour.
Measure infrared spectra and the gel permeation chromatography of the paste polymerisate that the present embodiment obtains, result shows, the paste polymerisate obtained in the present embodiment is the polyaniline of macromolecular structure.
The polyaniline obtained the present embodiment below does Corrosion Protection test, and test process is as follows:
Get an iron plate, be applied to after the polyaniline of the present embodiment is mixed with epoxy resin and isophorone diamine on this iron plate; Iron plate after smearing is placed in vacuum drying oven and heats 3h, obtain the first coating iron plate.Separately get an identical iron plate, at the mixture of this iron plate surface smear epoxy resin and isophorone diamine, be then placed in vacuum drying oven and heat 3h, obtain the second coating iron plate.
It should be noted that, the coat-thickness of the first coating iron plate is equal with the coat-thickness of the second coating iron plate.
Above-mentioned first coating iron plate and the second coating iron plate are done salt-fog test.At 5wt.%NaCl, pH value is under the salt fog of solution formation of 6.5 ~ 7.2, temperature maintains 35 ± 1.7 DEG C, scratching is done to the coatingsurface of the first coating iron plate and the second coating iron plate, continuous exposure experiment 240h, can find that the degree that weathers of the second coating iron plate is far above the first coating iron plate.It can thus be appreciated that the polyaniline that the present embodiment obtains has excellent Corrosion Protection.
Embodiment 6
(1) hydrochloric acid soln of preparation containing 1 molar part HCl, adds 8 molar part ammonium persulphates, obtains the first solution after stirring, regulate the pH of the first solution to be 1 in this hydrochloric acid soln;
(2) hydrochloric acid soln of preparation containing 40 molar part HCl, adds 2 molar part aniline and the adjacent pentanoic of 2 molar part, obtains the second solution, regulate the pH of the second solution to be 1 after stirring in this hydrochloric acid soln;
(3) water-bath the first solution and the second solution being placed in respectively 2 DEG C leaves standstill precooling;
(4) keep the temperature of 2 DEG C, the first solution after precooling is slowly joined in the second solution after precooling, leave standstill and obtain paste polymerisate after 1 hour.
Measure infrared spectra and the gel permeation chromatography of the paste polymerisate that the present embodiment obtains, result shows, the paste polymerisate obtained in the present embodiment is the polyaniline of macromolecular structure.
The polyaniline obtained the present embodiment below does Corrosion Protection test, and test process is as follows:
Get an iron plate, be applied to after the polyaniline of the present embodiment is mixed with epoxy resin and isophorone diamine on this iron plate; Iron plate after smearing is placed in vacuum drying oven and heats 3h, obtain the first coating iron plate.Separately get an identical iron plate, at the mixture of this iron plate surface smear epoxy resin and isophorone diamine, be then placed in vacuum drying oven and heat 3h, obtain the second coating iron plate.
It should be noted that, the coat-thickness of the first coating iron plate is equal with the coat-thickness of the second coating iron plate.
Above-mentioned first coating iron plate and the second coating iron plate are done salt-fog test.At 5wt.%NaCl, pH value is under the salt fog of solution formation of 6.5 ~ 7.2, temperature maintains 35 ± 1.7 DEG C, scratching is done to the coatingsurface of the first coating iron plate and the second coating iron plate, continuous exposure experiment 240h, can find that the degree that weathers of the second coating iron plate is far above the first coating iron plate.It can thus be appreciated that the polyaniline that the present embodiment obtains has excellent Corrosion Protection.
Embodiment 7
(1) hydrochloric acid soln of preparation containing 1 molar part HCl, adds 10 molar part Sodium Persulfates, obtains the first solution after stirring, regulate the pH of the first solution to be 3 in this hydrochloric acid soln;
(2) hydrochloric acid soln of preparation containing 80 molar part HCl, adds 5 molar part aniline and 2 molar part anthranilic acids, obtains the second solution after stirring, regulate the pH of the second solution to be 3 in this hydrochloric acid soln;
(3) water-bath the first solution and the second solution being placed in respectively 2 DEG C leaves standstill precooling;
(4) keep the temperature of 2 DEG C, the first solution after precooling is slowly joined in the second solution after precooling, leave standstill and obtain paste polymerisate after 1 hour.
Measure infrared spectra and the gel permeation chromatography of the paste polymerisate that the present embodiment obtains, result shows, the paste polymerisate obtained in the present embodiment is the polyaniline of macromolecular structure.
The polyaniline obtained the present embodiment below does Corrosion Protection test, and test process is as follows:
Get an iron plate, be applied to after the polyaniline of the present embodiment is mixed with epoxy resin and isophorone diamine on this iron plate; Iron plate after smearing is placed in vacuum drying oven and heats 3h, obtain the first coating iron plate.Separately get an identical iron plate, at the mixture of this iron plate surface smear epoxy resin and isophorone diamine, be then placed in vacuum drying oven and heat 3h, obtain the second coating iron plate.
It should be noted that, the coat-thickness of the first coating iron plate is equal with the coat-thickness of the second coating iron plate.
Above-mentioned first coating iron plate and the second coating iron plate are done salt-fog test.At 5wt.%NaCl, pH value is under the salt fog of solution formation of 6.5 ~ 7.2, temperature maintains 35 ± 1.7 DEG C, scratching is done to the coatingsurface of the first coating iron plate and the second coating iron plate, continuous exposure experiment 240h, can find that the degree that weathers of the second coating iron plate is far above the first coating iron plate.It can thus be appreciated that the polyaniline that the present embodiment obtains has excellent Corrosion Protection.
Embodiment 8
(1) hydrochloric acid soln of preparation containing 5 molar part HCl, adds 30 molar part ammonium persulphates, obtains the first solution after stirring, regulate the pH of the first solution to be 6 in this hydrochloric acid soln;
(2) hydrochloric acid soln of preparation containing 60 molar part HCl, adds 3 molar part aniline and the adjacent cyano-aniline of 2 molar part, obtains the second solution, regulate the pH of the first solution to be 6 after stirring in this hydrochloric acid soln;
(3) ice bath the first solution and the second solution being placed in respectively 0 DEG C leaves standstill precooling;
(4) keep the temperature of 0 DEG C, the first solution after precooling is slowly joined in the second solution after precooling, leave standstill and obtain paste polymerisate after 1 hour.
Measure infrared spectra and the gel permeation chromatography of the paste polymerisate that the present embodiment obtains, result shows, the paste polymerisate obtained in the present embodiment is the polyaniline of macromolecular structure.
The polyaniline obtained the present embodiment below does Corrosion Protection test, and test process is as follows:
Get an iron plate, be applied to after the polyaniline of the present embodiment is mixed with epoxy resin and isophorone diamine on this iron plate; Iron plate after smearing is placed in vacuum drying oven and heats 3h, obtain the first coating iron plate.Separately get an identical iron plate, at the mixture of this iron plate surface smear epoxy resin and isophorone diamine, be then placed in vacuum drying oven and heat 3h, obtain the second coating iron plate.
It should be noted that, the coat-thickness of the first coating iron plate is equal with the coat-thickness of the second coating iron plate.
Above-mentioned first coating iron plate and the second coating iron plate are done salt-fog test.At 5wt.%NaCl, pH value is under the salt fog of solution formation of 6.5 ~ 7.2, temperature maintains 35 ± 1.7 DEG C, scratching is done to the coatingsurface of the first coating iron plate and the second coating iron plate, continuous exposure experiment 240h, can find that the degree that weathers of the second coating iron plate is far above the first coating iron plate.It can thus be appreciated that the polyaniline that the present embodiment obtains has excellent Corrosion Protection.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for polyaniline, is characterized in that, comprises the following steps:
Obtain solution: mixed with oxygenant by inorganic acid aqueous solution, obtains the first solution; Inorganic acid aqueous solution is mixed with aniline monomer, obtains the second solution;
Precooling: described first solution and described second solution are adjusted to temperature of reaction respectively and carry out precooling;
Reaction: keep temperature of reaction, slowly joined by the first solution after described precooling in the second solution after described precooling, obtains paste polyaniline after leaving standstill 0.5h ~ 3h.
2. the preparation method of polyaniline according to claim 1, is characterized in that, described temperature of reaction is 0 DEG C ~ 10 DEG C.
3. the preparation method of polyaniline according to claim 1, is characterized in that, the mol ratio of the aniline monomer in the oxygenant in described first solution and described second solution is (1 ~ 10): 1.
4. the preparation method of polyaniline according to claim 1, is characterized in that, in described first solution, the mol ratio of described mineral acid and described oxygenant is 1:(5 ~ 15).
5. the preparation method of polyaniline according to claim 1, is characterized in that, in described second solution, the mol ratio of described mineral acid and described aniline monomer is (5 ~ 15): 1.
6. the preparation method of polyaniline according to claim 1, is characterized in that, before described precooling step, further comprising the steps of:
Regulate pH value to 1 ~ 4 of described first solution and described second solution respectively.
7. the preparation method of polyaniline according to claim 1, is characterized in that, described aniline monomer is the mixture of aniline or aniline and anils;
Described anils is one or more in methyl o-aminobenzoate, anthranilic acid, adjacent pentanoic, adjacent cyano-aniline, o-toluidine and Ortho-Chloro aniline.
8. the preparation method of polyaniline according to claim 1, is characterized in that, described mineral acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and boric acid.
9. the preparation method of polyaniline according to claim 1, is characterized in that, described oxygenant is one or more in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
10. a polyaniline, is characterized in that, described polyaniline adopts the preparation method of the polyaniline described in any one of claim 1 ~ 9 to be prepared from; Described polyaniline exists with cream form in aqueous phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410322605.2A CN105330855A (en) | 2014-07-08 | 2014-07-08 | Polyaniline and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410322605.2A CN105330855A (en) | 2014-07-08 | 2014-07-08 | Polyaniline and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105330855A true CN105330855A (en) | 2016-02-17 |
Family
ID=55281636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410322605.2A Pending CN105330855A (en) | 2014-07-08 | 2014-07-08 | Polyaniline and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105330855A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020009726A (en) * | 2000-07-26 | 2002-02-02 | 서갑수 | Process for producing a polyaniline and an apparatus for the same in large quantities |
| US20030161968A1 (en) * | 2002-02-27 | 2003-08-28 | Industrial Technology Research Institute | Method of enhancement of electrical conductivity for conductive polymer by use of field effect control |
| CN1733836A (en) * | 2005-08-26 | 2006-02-15 | 重庆大学 | Preparation method of epoxy/polyaniline composite base-material for anticorrosion paint |
| KR100642226B1 (en) * | 2005-06-22 | 2006-11-02 | 박진우 | Composition for preventing electrification and applied material using the same |
| CN102127223A (en) * | 2010-01-15 | 2011-07-20 | 北京化工大学 | Preparation method of micro/nano polyaniline |
| CN102775603A (en) * | 2012-07-12 | 2012-11-14 | 华东理工大学 | Preparation method of laminar polyaniline for anticorrosive paint |
-
2014
- 2014-07-08 CN CN201410322605.2A patent/CN105330855A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020009726A (en) * | 2000-07-26 | 2002-02-02 | 서갑수 | Process for producing a polyaniline and an apparatus for the same in large quantities |
| US20030161968A1 (en) * | 2002-02-27 | 2003-08-28 | Industrial Technology Research Institute | Method of enhancement of electrical conductivity for conductive polymer by use of field effect control |
| KR100642226B1 (en) * | 2005-06-22 | 2006-11-02 | 박진우 | Composition for preventing electrification and applied material using the same |
| CN1733836A (en) * | 2005-08-26 | 2006-02-15 | 重庆大学 | Preparation method of epoxy/polyaniline composite base-material for anticorrosion paint |
| CN102127223A (en) * | 2010-01-15 | 2011-07-20 | 北京化工大学 | Preparation method of micro/nano polyaniline |
| CN102775603A (en) * | 2012-07-12 | 2012-11-14 | 华东理工大学 | Preparation method of laminar polyaniline for anticorrosive paint |
Non-Patent Citations (2)
| Title |
|---|
| 刘霖: "导电聚苯胺的合成及其在电解电容器中的应用", 《中国优秀博硕士论文全文数据库（硕士） 工程科技Ⅱ辑》 * |
| 四川省纳米技术协会: "《纳米材料技术研发与应用》", 29 February 2012, 电子科技大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Trchová et al. | Evolution of polyaniline nanotubes: the oxidation of aniline in water | |
| Yang et al. | Synthesis of electroactive Tetraaniline− PEO− Tetraaniline triblock copolymer and its self-assembled vesicle with acidity response | |
| CN103059258A (en) | Organosilicon modified aqueous polyurethane emulsion | |
| CN101948561A (en) | Organic/inorganic silicon hybrid resin for coating and preparation method thereof | |
| CN106432568B (en) | The preparation method of Yi Zhong Duo oxazolinyl chain extenders | |
| Banerjee et al. | Amino‐Acid‐Based Zwitterionic Polymer and Its Cu (II)‐Induced Aggregation into Nanostructures: A Template for CuS and CuO Nanoparticles | |
| Zhao et al. | Polyaniline/graphene nanocomposites synthesized by in situ high gravity chemical oxidative polymerization for supercapacitor | |
| CN105712865B (en) | Solid citric acid aluminum crosslinker, preparation method and its application | |
| Zhou et al. | Chiral conducting polymer nanomaterials: synthesis and applications in enantioselective recognition | |
| CN103694379A (en) | Diblock copolymer with light and pH response characteristics and preparation method thereof | |
| CN106366249B (en) | The preparation method of carbon dioxide-base aquosity polyurethane-polyacrylate composite emulsion and its composite coating and they | |
| CN109679017B (en) | Single-component aqueous acrylic acid dispersion and preparation method thereof | |
| CN105331054A (en) | Composite conductive film | |
| CN103396722A (en) | Aqueous UV (ultraviolet)-curable fluorine-alcohol-modified epoxy resin coating and preparation method thereof | |
| CN101338030A (en) | Method for preparing nano-polymers of hydroxyl sulfoacid phenylamine and pyrrole | |
| CN108976354A (en) | A kind of environmentally friendly type polyurethane complex thickener and preparation method thereof of associating | |
| CN102344516A (en) | (Alkyl)fluoroalkyl acrylate polymer containing terminal alkyl ester or terminal carboxylic acid, its preparation and application | |
| CN105330855A (en) | Polyaniline and preparation method thereof | |
| Tanaka et al. | Design of metal salt/amide-based deep eutectic monomers toward sustainable production of ion-conductive polymers by radical polymerization | |
| CN101798453A (en) | Method for preparing water-borne functional polyurethane elastic emulsion | |
| CN106589280A (en) | Silicon-modified hyperbranched polyurethane and preparation method thereof | |
| CN102898592A (en) | Preparation method for acrylate-modified waterborne polyurethane | |
| CN114672023B (en) | Preparation method of flexible hyperbranched water-soluble polyimide resin | |
| CN102399416A (en) | Polyether poly(3,4-ethylenedioxythiophene) (PEDOT) water dispersion and preparation method thereof | |
| CN104988478A (en) | Metal surface treatment agent for gelatinous film and preparation method of metal surface treatment agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160217 |