CN1869101A - Proparation technology of conductive polyaniline - Google Patents

Proparation technology of conductive polyaniline Download PDF

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CN1869101A
CN1869101A CN 200610019480 CN200610019480A CN1869101A CN 1869101 A CN1869101 A CN 1869101A CN 200610019480 CN200610019480 CN 200610019480 CN 200610019480 A CN200610019480 A CN 200610019480A CN 1869101 A CN1869101 A CN 1869101A
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electrically conductive
polyaniline
preparing
monomer
conductive polyaniline
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CN100389141C (en
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顾卡丽
王颖
李健
高万振
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WUHAN INST OF MATERIAL PROTECTION
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Abstract

A electrically conductive polyphenylamine with high solubility, mechanical performance and adhesion is prepared from the hydroxyalkylthio ring substituted phenylamine and the siloxyalkylthio ring substituted phenylamine through copolymerizing under existence of oxidant and long-chain alkylprotonic acid.

Description

But a kind of technology of preparing of electrically conductive polyaniline
Technical field
But the present invention relates to the technology of preparing of conducting polymer composite, but particularly a kind of technology of preparing of electrically conductive polyaniline.
Background technology
Compare with other conducting polymer materials with long-chain conjugated structure, the polyaniline cost of material is cheap, synthesis technique is simple, and mechanism of doping effect is special, has a good application prospect.Based on the application of polyaniline photoelectric properties mainly be to replace conventional metals electro-conductive material, plane display material, fields such as machine electrode, secondary cell, erosion shield, antistatic material (ESD), coating for EMI shielding (EMI), Electro-Discolor Coating, photodiode, optics and device for non-linear optical are arranged, require more extensive than overall applicability of the polyaniline used with coating form.But known because the strong rigidity of polyaniline chain and strong chain interphase interaction, the polyaniline secondary workability is poor, infusibility indissoluble, film forming difficulty, and institute's film forming is very poor with the sticking power of ground and plane materiel, the also non-constant of mechanical property has a strong impact on the practicability of polyaniline material.
Existing many documents, for example (Zhiming Zhang, et al.Nanostructures of Polyaniline Dopedwith Inorganic Acids.Macromolecules.2002,35,5937-5942; Wusheng Yin, et al.Water-So-luble Self-Doped Conducting Polyaniline Copolymer.Macromolecules.2000,33,1129-1131; Liu Shaoqiong etc. property of polyaniline doped with camphor sulfonic acid. functional materials .2001,5,512-513.) and patent (US6194540; US5993694; US5891970; CN1415645A; CN1030243A; CN1718611A; N1667020A; CN1202499A) etc., do a lot of work for the processibility and the solvability that improve polyaniline.But above document and patent all only are conceived to improve the solvability of polyaniline, and have ignored the mechanical property of polyaniline material, and gained polyaniline coating mechanical strength is low, sticking power is very poor, can erase easily with finger.And because doping agent and substituent space steric effect, all means of attempting to increase the layer/polyaniline conductive rate are cost to sacrifice its electric conductivity all at present.
Polyaniline must satisfy certain mechanical property, reaches certain sticking power, could satisfy normal industrial needs.
The objective of the invention is to utilize suitable substituted radical and doping agent to prepare the high conductivity polyaniline, make it be soluble in general, cheap, hypotoxic solvent, especially make polyaniline coating have good mechanical intensity and sticking power.
Summary of the invention
Purpose of the present invention reaches by selecting following monomer and synthesis technique:
(1) a certain proportion of alcohol is placed reaction vessel as reaction medium, add the organic proton acid-conditioning solution of a certain amount of macromole pH value to 0～3, the aromatic amine that adds following a kind of hydroxyl alkylthio (or hydroxy alkoxy base) more successively is a monomer A,
With following a kind of aromatic amine with the silica coupling group be monomers B,
Agitation and dropping reaction medium alcohol institute dissolved oxygenant under condition of nitrogen gas is in 0～5 ℃ of reaction 2～6 hours, in room temperature reaction 10～30 hours;
(2) with the reaction residual suction filtration in (1), but room temperature vacuum-drying after 2～5 hours the gained solid be indication electrically conductive polyaniline of the present invention.
The ratio control of monomer A and monomers B is between 10: 1～100 during above-mentioned polyreaction, and ratio is between 5: 1～25 preferably.The oxygenant that drips can be Potassium Persulphate, ammonium persulphate etc., and oxygenant and monomeric mol ratio are controlled between 0.5～2.Said macromole protonic acid is selected from hexyl sulfonic acid, heptyl sulfonic acid, octyl group sulfonic acid, dodecyl sodium sulfonate etc.The reaction medium alcohol that is adopted in the polymerization is selected from ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol etc.
Synthon A used in the present invention and B have following feature
(1) monomer A, its general formula is
R wherein 1, R 2, R 3, R 4, R 5In any and several be hydroxyl alkylthio group, all the other can be respectively-H-OH ,-OCH 3,-OCH 2CH 3, the general structure of the alkylthio group that this is hydroxyl is
-SC nH 2n+1-m(OH) m
N can be the arbitrary integer greater than 3 in the formula, and m can be greater than 1 arbitrary integer less than 2n,
(2) monomers B, its general formula is:
Figure A20061001948000062
R wherein 1, R 2, R 3, R 4, R 5In any or several are alkylthio groups of band siloxanes, all the other can be respectively-H ,-OH ,-OCH 3,-OCH 2CH 3, this hydroxyl alkylthio unit structure general formula is:
-SC nH 2n+1R′
N can be for more than or equal to 2 integer in the formula.R ' is the siloxanes coupling group, can be selected from:
Figure A20061001948000071
Compare with other inventions, the present invention has following distinct advantages: (1) introduces polyaniline so as to increasing the sticking power of polyaniline and low layer (or upper strata) with coupling group; (2) introducing hydroxyl on the alkyl branches increases the solubleness of polyaniline in polarity and non-polar solvent simultaneously, to reach the purpose of use same solvent when cooperating with resins for universal use; (3) on the aniline ring, introduce long hydroxyl alkylthio side chain, for example-S-(CH 2) 12OH is to increase polyaniline interchain entanglement degree; (4) with sterically hindered less chain alkyl sulfonic acid, for example hexyl sulfonic acid, heptyl sulfonic acid, octyl group sulfonic acid or dodecyl sodium sulfonate, p-poly-phenyl amine mixes; (5) can be adjusted in the quantity of alkyl chain length and hydroxyl on the monomer A and come the relative solvability of controlling polymers in polarity and non-polar solvent; (6) size and the conductive capability size of the power of sticking power, solubleness regulated in monomer A and monomers B random copolymerization, the ratio that can regulate A and B.
The invention has the beneficial effects as follows: have higher electric conductivity according to the prepared polyaniline that goes out of invention, in industrial solvents commonly used such as toluene, dimethylbenzene, chloroform, butanone, acetone, vinyl acetic monomer, N-BUTYL ACETATE, have good solubility.The more important thing is, film after being dissolved in above solvent according to the prepared polyaniline that goes out of the present invention, treat solvent evaporates after the gained coating have good mechanical intensity and sticking power.
Specific implementation method
Following embodiment just further specifies of the present invention, rather than limit it.
Embodiment one:
There-necked flask is placed 5 ℃ of water-baths, in there-necked flask, add a certain amount of macromole protonic acid dodecyl sodium sulfonate in 150.0ml ethanol, regulate about pH value to 0.5, add successively again between monomer A 7.3g-(5-hydroxyl butylthio) aniline, between monomers B 10.0g-(the silica-based ethylmercapto group of 3-trimethoxy) aniline.9.9g oxygenant Potassium Persulphate is dissolved in the dehydrated alcohol, and under nitrogen protection and agitation condition, slowly is added dropwise to there-necked flask, drip in half hour and finish, remain on 5 ℃ of reactions 4 hours after dripping, reacted at ambient temperature 15 hours.Carry out suction filtration after reaction is finished, but promptly got electrically conductive polyaniline in 2 hours in drying at room temperature then.But the gained electrically conductive polyaniline is dissolved in dimethylbenzene: the mixed solvent of butanols=60: 40, the spraying back is at 60 ℃ of following drying and forming-films.
Embodiment two:
There-necked flask is placed 5 ℃ of water-baths, in there-necked flask, add a certain amount of macromole protonic acid octyl group sulfonic acid and in the 150.0ml n-propyl alcohol, regulate about pH value to 0.5, add successively again between monomer A 9.7g-(5-hydroxyl butylthio) aniline, between monomers B 6.7g-(2-dimethoxy ethyl-silicone ethylmercapto group) aniline.19.7g oxygenant Potassium Persulphate is dissolved in the anhydrous n-propyl alcohol, and under nitrogen protection and agitation condition, slowly is added dropwise to there-necked flask, drip in half hour and finish, remain on 5 ℃ of reactions 4 hours after dripping, reacted at ambient temperature 15 hours.Carry out suction filtration after reaction is finished, but promptly got electrically conductive polyaniline in 2 hours in room temperature vacuum-drying then.But the gained electrically conductive polyaniline is dissolved in dimethylbenzene: the mixed solvent of butanols=60: 40, after the spraying film forming at 60 ℃ of following drying and forming-films.
Embodiment three:
There-necked flask is placed ice-water bath, in there-necked flask, add a certain amount of macromole protonic acid heptyl sulfonic acid and in the 150.0ml Virahol, regulates about pH value to 0.5, add successively again between monomer A 9.4g-(9-hydroxyl suffering sulfenyl) aniline, between monomers B 10.5g-(4-dimethoxy ethyl-silicone butylthio) aniline.19.8g oxygenant Potassium Persulphate is dissolved in the anhydrous isopropyl alcohol, and under nitrogen protection and agitation condition, slowly is added dropwise to there-necked flask, drip in half hour and finish, remain on 0 ℃ of reaction 4 hours after dripping, reacted at ambient temperature 20 hours.Carry out suction filtration after reaction is finished, suction filtration gained filter residue was promptly got electrically conductive polyaniline in 5 hours in room temperature vacuum-drying.The gained polyaniline is dissolved in dimethylbenzene: the mixed solvent of butanols=60: 40, the spraying back is at 60 ℃ of following drying and forming-films.
Embodiment four:
There-necked flask is placed ice-water bath, in there-necked flask, add a certain amount of macromole protonic acid dodecyl sodium sulfonate and in the 150.0ml propyl carbinol, regulates about pH value to 0.5, add successively again between monomer A 9.4g-(9-hydroxyl suffering sulfenyl) aniline, between monomers B 10.8g-(the silica-based butylthio of 4-three ethoxies) aniline.17.5g oxygenant ammonium persulphate is dissolved in the anhydrous normal butyl alcohol, and under nitrogen protection and agitation condition, slowly is added dropwise to there-necked flask, drip in half hour and finish, remain on 0 ℃ of reaction 4 hours after dripping, reacted at ambient temperature 20 hours.Carry out suction filtration after reaction is finished, but suction filtration gained filter residue was promptly got electrically conductive polyaniline in 5 hours in room temperature vacuum-drying.But the gained electrically conductive polyaniline is dissolved in dimethylbenzene: the mixed solvent of butanols=60: 40, the spraying back is 60 ℃ of down dry 4 hours film forming.
Embodiment five:
There-necked flask is placed ice-water bath, in there-necked flask, add a certain amount of macromole protonic acid octyl group sulfonic acid and in the 150.0ml isopropylcarbinol, regulate about pH value to 0.5, add successively again between monomer A 11.4g-(9-hydroxyl dodecane sulfenyl)-aniline, between monomers B 14.6g-(the silica-based dodecane sulfenyl of 12-three ethoxies) aniline.25.1g oxygenant ammonium persulphate is dissolved in the dry isobutanol, and under nitrogen protection and agitation condition, slowly is added dropwise to there-necked flask, drip in half hour and finish, remain on 0 ℃ of reaction 4 hours after dripping, reacted at ambient temperature 20 hours.Carry out suction filtration after reaction is finished, but suction filtration gained filter residue was promptly got electrically conductive polyaniline in 5 hours in room temperature vacuum-drying.But the gained electrically conductive polyaniline is dissolved in dimethylbenzene: the mixed solvent of butanols=60: 40, the spraying back is 60 ℃ of down dry 4 hours film forming.
Embodiment six:
There-necked flask is placed ice-water bath, in there-necked flask, add a certain amount of macromole protonic acid hexyl sulfonic acid and in the 150.0ml primary isoamyl alcohol, regulates about pH value to 0.5, add successively again between monomer A 6.2g-(8-hydroxyl suffering sulfenyl) aniline, between monomers B 22.2g-(the silica-based dodecane sulfenyl of 12-three ethoxies) aniline.16.7g oxygenant ammonium persulphate is dissolved in the anhydrous primary isoamyl alcohol, and under nitrogen protection and agitation condition, slowly is added dropwise to there-necked flask, drip in half hour and finish, remain on 0 ℃ of reaction 4 hours after dripping, reacted at ambient temperature 20 hours.Carry out suction filtration after reaction is finished, but suction filtration gained filter residue was promptly got electrically conductive polyaniline in 5 hours in room temperature vacuum-drying.But the gained electrically conductive polyaniline is dissolved in dimethylbenzene: the mixed solvent of butanols=60: 40, the spraying back is 60 ℃ of down dry 4 hours film forming.
But the made electrically conductive polyaniline film of above embodiment all reaches the described performance of purpose of the present invention.

Claims (6)

  1. But the technology of preparing of 1 one kinds of electrically conductive polyanilines is characterized in that following two kinds of polymerization single polymerization monomer A and B adding are contained in the alcoholic solvent of macromole protonic acid, and dropping oxidizing agent generation copolymerization is drying to obtain electrically conductive polyaniline but reaction finishes the back separation:
    (1) monomer A, its general formula is
    R wherein 1, R 2, R 3, R 4, R 5In any and several be hydroxyl alkylthio group, all the other can be respectively-H-OH-OCH 3-OCH 2CH 3The general structure of the alkylthio group that this is hydroxyl is
    -SC nH 2n+1-m(OH) m
    N can be the arbitrary integer greater than 3 in the formula, and m can be greater than 1 arbitrary integer less than 2n,
    (2) monomers B, its general formula is:
    R wherein 1, R 2, R 3, R 4, R 5In any or several be the band siloxanes the alkylthio group, all the other can be distinguished-H-OH-OCH 3-OCH 2CH 3, this hydroxyl alkylthio unit structure general formula is:
    -SC nH 2n+1R′
    N can be for greater than 2 or the integer that equals in the formula.R ' is the siloxanes coupling group, is selected from:
    Figure A2006100194800003C1
    Deng.
  2. But 2 a kind of technologies of preparing of electrically conductive polyaniline according to claim 1 is characterized in that used oxygenant can be a Potassium Persulphate, ammonium persulphate etc., and oxygenant and monomeric mol ratio are controlled between 0.5～2.
  3. But 3 a kind of technologies of preparing of electrically conductive polyaniline according to claim 1 is characterized in that the ratio of monomer A and monomers B is between 10: 1～100 in the polymerization.
  4. But 4 a kind of technologies of preparing of electrically conductive polyaniline according to claim 1, the solvent that it is characterized in that in the polymerization being adopted is selected from ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol etc.
  5. But 5 a kind of technologies of preparing of electrically conductive polyaniline according to claim 1 is characterized in that the macromole protonic acid that is adopted is selected from hexyl sulfonic acid, heptyl sulfonic acid, octyl group sulfonic acid, dodecyl sodium sulfonate etc.
  6. But the technology of preparing of 6 a kind of electrically conductive polyanilines as claimed in claim 1, it is characterized in that prepared polyaniline dissolves in the mixed solvent of toluene, dimethylbenzene, chloroform, butanone, acetone, vinyl acetic monomer, N-BUTYL ACETATE and above solvent, use this solution coating, treat that solvent evaporates obtains polyaniline film.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875813A (en) * 2012-08-14 2013-01-16 苏州大学 Polysiloxane modified polyaniline and preparation method thereof

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* Cited by examiner, † Cited by third party
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TW464661B (en) * 1996-06-10 2001-11-21 Nippon Catalytic Chem Ind Water-soluble electrically-conductive polyaniline and method for production thereof and antistatic agent using water-soluble electrically-conductive polymer
TW502046B (en) * 1998-10-22 2002-09-11 Nippon Catalytic Chem Ind Method for production of water-soluble conducting polyaniline
CN1718611A (en) * 2005-08-04 2006-01-11 上海应用技术学院 Preparation method of conductive polyaniline

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102875813A (en) * 2012-08-14 2013-01-16 苏州大学 Polysiloxane modified polyaniline and preparation method thereof
CN102875813B (en) * 2012-08-14 2014-09-17 苏州大学 Polysiloxane modified polyaniline and preparation method thereof

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