CN104927052A - Method for preparing polyaniline solution in organic solvent - Google Patents
Method for preparing polyaniline solution in organic solvent Download PDFInfo
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- CN104927052A CN104927052A CN201510340156.9A CN201510340156A CN104927052A CN 104927052 A CN104927052 A CN 104927052A CN 201510340156 A CN201510340156 A CN 201510340156A CN 104927052 A CN104927052 A CN 104927052A
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Abstract
The invention belongs to the technical field of high molecular material synthesis, and particularly relates to a method for preparing a polyaniline solution in organic solvent. The method includes the steps that 1, monomer aniline or an aniline derivative and organic acid are dissolved in the first organic solvent to obtain monomer organic solvent; 2, an initiator is added into the monomer organic solvent obtained in the step 1, the components react under the condition of ultrasonic wave radiation to obtain the polyaniline solution, or the initiator is dissolved in second organic solvent, the components react under the condition of ultrasonic wave radiation to obtain the polyaniline solution. The method for preparing the polyaniline solution in the organic solvent has the advantages that a reaction system is in full oil phase, and no water is involved. The polyaniline solution obtained through preparation is composed of conductive polyaniline, the solvent and reduction products of organic peroxides, wherein the reduction products of the organic peroxides can be dissolved in the solvent to serve as organic packing, and it is avoided that use in the next step is affected, and performance is reduced.
Description
Technical field
The invention belongs to the synthesis technical field of macromolecular material, particularly relate to a kind of method preparing polyaniline solutions in organic solvent.
Background technology
Paint most at present and ink mostly are oleaginous system, the necessary desalination of polyaniline of the synthesis condition polymerization participated in there being water, dehydration, tretolite, purifying, directly cannot add the paint of oiliness or ink or water-borne coatings, because reaction solution is containing emulsifying agent by the polyaniline liquid that the synthesis condition having water to participate in is polymerized, a large amount of inorganic salt, produce serious disadvantageous effect to paint and coating property.
Summary of the invention
For solving the deficiencies in the prior art: polyaniline aftertreatment can be reunited, twice dispersing is difficult, and waste amount is large, the invention provides a kind of method preparing polyaniline solutions in organic solvent.By the method, the polyaniline solutions that homogeneity is good can be obtained, not need to isolate polyaniline (polyaniline can not be reunited, without waste), just can be directly used in the preparation of the material such as coating and ink.There is good dispersity, step of preparation process is few, can directly be used and avoid the advantages such as polyaniline secondary agglomeration.For the nano application of polyaniline lays the foundation.Do not produce waste.There is environmental protection and energy saving feature.
Prepare a method for polyaniline solutions in organic solvent, comprise the steps:
1) derivative of monomer aniline or aniline and organic acid are dissolved in the first organic solvent, obtain monomer organic solvent.
Concrete, step 1) described in the structural formula of derivative of aniline as follows:
Wherein, R is selected from hydrogen, methyl, ethyl or halogen.Halogen is preferably chlorine or bromine.
Concrete, step 1) described in organic acid be selected from any one or multiple mixing in alkyl benzene sulphonate (ABS), alkylsurfuric acid, alkylphosphonic acid carboxylic acid or alkyl carboxylic acid.
Preferred:
Described alkyl benzene sulphonate (ABS) to be carbonatoms be 2 ~ 18 alkyl or haloalkyl Phenylsulfonic acid;
Described alkylsurfuric acid to be carbonatoms be 2 ~ 18 alkyl or haloalkyl sulfuric acid;
Described alkylphosphonic acid carboxylic acid to be carbonatoms be 2 ~ 18 alkyl or haloalkyl phosphoric acid;
Described alkyl carboxylic acid to be carbonatoms be 2 ~ 18 alkyl or alkylcarboxylic acid.
2) initiator is joined step 1) in the monomer organic solvent that obtains, react under Ultrasonic Radiation condition and under the temperature condition of 0 ~ 30 DEG C, obtain polyaniline solutions, or, initiator is dissolved in the second organic solvent, obtains initiator organic solvent, then initiator organic solvent is mixed with described monomer organic solvent, react under Ultrasonic Radiation condition and under the temperature condition of 0 ~ 30 DEG C again, obtain polyaniline solutions.
Concrete, the reaction times is 24 ~ 48 hours.
Concrete, step 2) described in initiator be organo-peroxide.Organo-peroxide can be selected from acyl class superoxide, hydroperoxide, dialkyl peroxide, ester class superoxide, ketone superoxide, two carbonic ether superoxide or percarboxylic acids any one.
Preferred:
Acyl class superoxide is selected from benzoyl peroxide etc.;
Hydroperoxide are selected from the different phenylpropyl alcohol of hydrogen peroxide etc.;
Dialkyl peroxide is selected from dicumyl peroxide etc.;
Peroxy esters class is selected from any one or multiple mixing in peroxide new enanthic acid 1,1-dimethyl-3-hydroxy butyl ester, peroxidation neodecanoic acid, isopropyl phenyl ester, peroxidation neodecanoic acid tert-pentyl ester, t-butylperoxy pivarate, peroxybenzoic acid tert-pentyl ester or t-butylperoxyl benzoate, t-butyl peroxy ketal or t-amyl peroxy ketal etc.;
Ketone superoxide is selected from methyl ethyl ketone peroxide etc.;
Peroxydicarbonate is selected from 2-ethylhexyl peroxy dicarbonate etc.;
Percarboxylic acids is selected from perbenzoic acid etc.
Above, step 1) described in the first organic solvent be arene, fat hydrocarbon, alicyclic hydrocarbon type, halogenated hydrocarbon, alcohols, ethers, ester class, ketone, alcohol ethers, nitrile or carboxylic-acid with the second described organic solvent, described first organic solvent and described second organic solvent can select identical component, also can select race's different components.
Concrete, arene be selected from benzene,toluene,xylene etc. any one; Fat hydrocarbon be selected from pentane, hexane, octane etc. any one; Alicyclic hydrocarbon type be selected from hexanaphthene, pimelinketone, toluene pimelinketone etc. any one; Halogenated hydrocarbon be selected from chlorobenzene, dichlorobenzene, methylene dichloride etc. any one; Alcohols be selected from methyl alcohol, ethanol, Virahol etc. any one; Ethers be selected from ether, propylene oxide etc. any one; Ester class be selected from ritalin, vinyl acetic monomer, propyl acetate etc. any one; Ketone be selected from acetone, espeleton, mibk etc. any one; Alcohol ethers is diol, derivatives, is selected from any one in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether etc.; Nitrile is acetonitrile etc.; Carboxylic-acid be selected from formic acid, acetic acid etc. any one.
On the one hand, the feature preparing the method for polyaniline solutions in organic solvent provided by the present invention is not relate to water in reaction system, is full oil phase.The polyaniline solutions prepared by the method preparing polyaniline solutions in organic solvent provided by the present invention consist of electrically conductive polyaniline, solvent, organo-peroxide reduzate.Organo-peroxide reduzate wherein can dissolve in a solvent, as organic filler, does not affect next step and uses and performance reduction.
On the other hand, polymerization polyaniline solutions of the present invention adopts organo-peroxide, and system is saliferous not, emulsifying agent, does not need traditional post-treatment method.Can be applied directly in coating and printing ink making processes and go.Economize the breakdown of emulsion that the polyaniline of the synthesis condition polymerization having water to participate in is necessary, desalination, dehydration, the process of tretolite, solves in breakdown of emulsion desalination, dehydration, in tretolite process, polyaniline must cause reunion, abraum salt, solves polyaniline in the application of polyaniline in paint and ink and is difficult to a difficult problem of disperseing, make the excellent properties of polyaniline be played and embody.
In addition, advantage of the present invention is also embodied in the aspect such as agglomeration and the feature of environmental protection of product.
Agglomeration aspect: original solution polyaniline is liquid state, and the particle diameter 10 ~ 30 microns of powder, meet the requirement of commercial polyaniline.
Feature of environmental protection aspect: traditional synthesis in water per kilogram polyaniline needs ammonium persulfate 3 ~ 6kg, emulsifying agent 0.1 ~ 2.5kg, water 50kg, assistant for emulsifying agent 0.1 ~ 0.5, this synthetic method can not need breakdown of emulsion, desalination, cleaning, reduce abraum salt 3 ~ 6kg, emulsifying agent 0.1 ~ 2.5kg, alcohol 5kg, water 50kg, reduce a large amount of artificial, spillage of material, the energy uses.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.Prove the evidence that viewpoint above needs.
Embodiment 1
0.1mol aniline, the Witco 1298 Soft Acid of 0.05mol, add 0.2mol dimethylbenzene, 0.5mol propyl carbinol high speed is stirred in 1000rpm and stirs 30min, until solution clarification, 10min adds the benzoyl peroxide solution (0.1mol benzoyl peroxide is dissolved into 0.3mol propyl carbinol) of 0.1mol, under 100 watts of power ultrasonic effects, react 24 hours, temperature controls at 25 DEG C.The conductive polyaniline solution obtained.Further, if need solid polyaniline, can get conductive polyaniline solution and dry, grinding obtains polyaniline powder.
In other examples, other disclosed in the present invention solvent selected respectively by solvent, and other disclosed in the present invention superoxide selected by initiator, and other reaction conditionss are constant, can obtain polyaniline powder equally.
By the conductive polyaniline solution 10 grams obtained, directly can add same moral vinylformic acid 1260 resin 45 grams and stir evenly, grinding can prepare other multiple products such as electrically conductive polyaniline varnish or ink.This varnish film can wait until the conducting film of 7 powers of 4.5*10.This varnish is according to GB salt mist experiment and blank resin model contrast contrast, and the salt fog time rose to 168 hours from 96 hours, performance boost 70%.
Embodiment 2
0.05mol aniline, adds 2.0mol acetic acid, and 0.03mol dodecyl sulphate adds 0.75mol hydrogen peroxide, high-speed stirring, and temperature controls at 25 DEG C, under 100 watts of hyperacoustic effects, can obtain polyaniline solutions and directly use.
In other examples, select disclosed in the present invention other solvent, organic acid, initiator, other reaction conditionss are constant, can prepare the polyaniline solutions that can directly use equally.
Embodiment 3
0.1mol o-toluidine, the dodecylphosphoric acid of 0.045mol, add 0.2mol dimethylbenzene, 0.5mol propyl carbinol high speed stirs, until solution clarification, drip the benzoyl peroxide solution (0.1mol benzoyl peroxide is dissolved into 0.3mol propyl carbinol) of 0.1mol, under 100 watts of power ultrasonic effects, react 24 ~ 48 hours, temperature controls at 0 ~ 30 DEG C.The solution obtained directly can add resin-made for other products such as coating or ink, can also wait until thick polyaniline by spraying dry, can wait until high-purity polyaniline through absolute ethanol washing.
In other enforcement, monomer selects m-toluidine, open-chain crown ether, o ethyl aniline, m-ethyl aniline, to ethylaniline etc., other reaction conditionss are constant, can prepare high-purity polyaniline equally.
The foregoing is only better embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. prepare a method for polyaniline solutions in organic solvent, it is characterized in that, comprise the steps:
1) derivative of monomer aniline or aniline and organic acid are dissolved in the first organic solvent, obtain monomer organic solvent;
2) initiator is joined step 1) in the monomer organic solvent that obtains, react under Ultrasonic Radiation condition and under the temperature condition of 0 ~ 30 DEG C, obtain polyaniline solutions; Or, initiator is dissolved in the second organic solvent, obtains initiator organic solvent, then initiator organic solvent is mixed with described monomer organic solvent, react under Ultrasonic Radiation condition and under the temperature condition of 0 ~ 30 DEG C again, obtain polyaniline solutions.
2. the method preparing polyaniline solutions in organic solvent according to claim 1, is characterized in that, step 1) described in the structural formula of derivative of aniline as follows:
Wherein, R is selected from hydrogen, methyl, ethyl or halogen.
3. the method preparing polyaniline solutions in organic solvent according to claim 1, is characterized in that: step 1) described in organic acid be selected from any one or multiple mixing in alkyl benzene sulphonate (ABS), alkylsurfuric acid, alkylphosphonic acid carboxylic acid or alkyl carboxylic acid.
4. the method preparing polyaniline solutions in organic solvent according to claim 3, is characterized in that:
Described alkyl benzene sulphonate (ABS) to be carbonatoms be 2 ~ 18 alkyl benzene sulphonate (ABS) or carbonatoms be 2 ~ 18 haloalkyl Phenylsulfonic acid;
Described alkylsurfuric acid to be carbonatoms be 2 ~ 18 alkyl or haloalkyl sulfuric acid;
Described alkylphosphonic acid carboxylic acid to be carbonatoms be 2 ~ 18 alkyl or haloalkyl phosphoric acid;
Described alkyl carboxylic acid to be carbonatoms be 2 ~ 18 alkyl or alkylcarboxylic acid.
5. the method preparing polyaniline solutions in organic solvent according to claim 1, is characterized in that: step 2) described in initiator be organo-peroxide.
6. the method preparing polyaniline solutions in organic solvent according to claim 5, is characterized in that: step 2) described in organo-peroxide be acyl class superoxide, hydroperoxide, dialkyl peroxide, ester class superoxide, ketone superoxide, two carbonic ether superoxide or percarboxylic acids.
7., according to the arbitrary described method preparing polyaniline solutions in organic solvent of claim 1 to 6, it is characterized in that:
Step 1) described in the first organic solvent be arene, fat hydrocarbon, alicyclic hydrocarbon type, halogenated hydrocarbon, alcohols, ethers, ester class, ketone, alcohol ethers, nitrile or carboxylic-acid;
Step 1) described in the second organic solvent be arene, fat hydrocarbon, alicyclic hydrocarbon type, halogenated hydrocarbon, alcohols, ethers, ester class, ketone, alcohol ethers, nitrile or carboxylic-acid;
Described first organic solvent and described second organic solvent identical or different.
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| CN201510340156.9A CN104927052A (en) | 2015-06-18 | 2015-06-18 | Method for preparing polyaniline solution in organic solvent |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141310A (en) * | 1995-07-27 | 1997-01-29 | 中国科学院长春应用化学研究所 | Method for preparing soluble aniline and derivatives with various molecular wt. |
| CN101139440A (en) * | 2007-10-17 | 2008-03-12 | 天津大学 | Method for preparing high-purity nano-sheet polyaniline |
| US20080142074A1 (en) * | 2003-10-08 | 2008-06-19 | The Yokohama Rubber Co., Ltd. | Method for producing conductive polyaniline |
| CN101492569A (en) * | 2008-07-01 | 2009-07-29 | 南京理工大学 | Oxidized graphite flake layer/polyaniline composite material and method for preparing the same |
-
2015
- 2015-06-18 CN CN201510340156.9A patent/CN104927052A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141310A (en) * | 1995-07-27 | 1997-01-29 | 中国科学院长春应用化学研究所 | Method for preparing soluble aniline and derivatives with various molecular wt. |
| US20080142074A1 (en) * | 2003-10-08 | 2008-06-19 | The Yokohama Rubber Co., Ltd. | Method for producing conductive polyaniline |
| CN101139440A (en) * | 2007-10-17 | 2008-03-12 | 天津大学 | Method for preparing high-purity nano-sheet polyaniline |
| CN101492569A (en) * | 2008-07-01 | 2009-07-29 | 南京理工大学 | Oxidized graphite flake layer/polyaniline composite material and method for preparing the same |
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Application publication date: 20150923 |