CN1209508C - Polyaniline/polyacrylonitrile composite conductive fibre and preparation process thereof - Google Patents
Polyaniline/polyacrylonitrile composite conductive fibre and preparation process thereof Download PDFInfo
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- CN1209508C CN1209508C CN 03116654 CN03116654A CN1209508C CN 1209508 C CN1209508 C CN 1209508C CN 03116654 CN03116654 CN 03116654 CN 03116654 A CN03116654 A CN 03116654A CN 1209508 C CN1209508 C CN 1209508C
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- polyaniline
- polyacrylonitrile
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Abstract
The present invention discloses a polyaniline/polyacrylonitrile composite conductive fibre and a preparation method thereof. The conductive fibre of the present invention is composed of organic sulfonate of polyaniline and polyacrylonitrile. Soluble polyaniline doped with organic sulfonic acid is firstly prepared; then the organic sulfonate of polyaniline and polyacrylonitrile are dissolved in a mixed solvent; the mixed solution is soaked over a spinning nozzle by wet spinning technology, and the mixed solution is squeezed in a coagulating bath; after being stretched and washed, the mixed solution is prepared into the conductive fibre. The conductivity of the fibre can be controlled in the range of 10 (-7)-10 (-1) (S/cm); the conductive fibre produced by the method of the present invention has good strength which is generally from 1.5 CN/tax to 3.4CN//tax, and the conductive fibre can meet the use requirements in the spinning field and other fields; the conductive fibre can be used as a semiconductor device, an electromagnetic shielding material and an antistatic material, can also absorb radar, infrared rays, ultraviolet rays, etc., and can be used in many special fields.
Description
Technical field
The present invention relates to a kind of conductive fiber, specifically, relate to a kind of polyaniline composite conducting fiber and preparation method thereof.
Background technology
Conducting polymer is the previous suitable active research of order field, has developed into the interdisciplinary science of macromolecule, electrochemistry and solid state physics.Polyaniline is compared with other conducting polymer, has strong, the electrical conductivity advantages of higher of easy, good at air and water stability, the charge storage ability of preparation, thereby causes domestic and international researcher's extensive attention, is considered to one of the most promising conducting polymer.
Synthetic, the electrical conduction mechanism of people's p-poly-phenyl amine, molecular structure etc. have carried out systematic research, have obtained the understanding of comparison unanimity in recent years, and the emphasis of research is just turning to application and development.Preparation layer/polyaniline conductive fiber is one of them important use field.Conductive fiber has purposes widely, aspect taking, a spot of conductive fiber can be sneaked into the common antistatic problem that can solve in the fibre in the fabric use of closing, and also can reduce static and inhale ash, plays dustproof effect; Industrial, conductive fiber can be used as semiconductor devices, electromagnetic shielding material and antistatic material etc.Except that the various uses with common conductive fiber, because the various premium properties that polyaniline had, polyaniline fiber also can be used for absorbing radar, infrared ray, ultraviolet ray etc., is applied to many special dimensions.
Because polyaniline can not fusion, generally takes solution spinning, so improve the key that the dissolubility of polyaniline in organic solvent is its machinability of solution.At present the polyaniline spinning process has two kinds of wet method and dry method, and in numerous spinning solution systems and coagulating agent system, the solvent that is used for spinning is dimethyl propylene urea and 1, the 4-cyclohexanediamine, but these two kinds of solvent prices are comparatively expensive.Polyaniline body conductive fiber requires height to solvent and spinning equipment in addition, and fibre strength is relatively poor, and fragility is big, and what therefore application prospect is arranged relatively is the polyaniline composite fibre.
Document: " Zhang Qinghua, Jin Huifen, the development of polyaniline/PA11 blend conductive fiber.Synthetic fiber, 2000,29 (4), 10-12 " reported that (be matrix polymer, the concentrated sulfuric acid is a spin solvent, and polyaniline is added in the spinning slurry as conductive agent, adopts wet spinning technology, is the conductive fiber that coagulating bath makes with water with nylon 11.Document: " Electronically-Conductive Fibers of Polyanline Spun from Solutions in ConcentratedSulfuric Acid, by Andreatta, Cao, Chiang, Heeger and Smith.SyntheticMetals, 26 (1988) 383-389. " reported the electrically conductive composite fibre that makes polyaniline and PPTA from the homogeneous phase solution of the concentrated sulfuric acid of polyaniline and PPTA (PPTA).The spin solvent that is adopted in the above-mentioned document all is the concentrated sulfuric acid, thereby the corrosion resistance of spinning equipment has been proposed harsh requirement, poor operability.
In recent years, document " Electron diffraction studies of the structure ofpolyaniline-dodecylbenzenesulfonate by Yang, C.Y.; Smith, P.; Heeger, A.J.; Cao, Y.; Osterholm, J.E.Polymer, 35 (1994) 1142-1147 and Solutioncharacterization of surfactant solubilized polyaniline by Gettinger, C.L.; Heeger, A.J.; Pine, D.J.; Cao, Y.Synthetic Metals, 74 (1995) 81-88 " when find selecting organic sulfonic acid that DBSA (DBSA), camphorsulfonic acid (CSA) etc. have nonpolar or a low pole group, can obtain being dissolved in the doped polyaniline in the usual vehicle as adulterant.But the technology that the document provides is only studied doped polyaniline, and it is relatively poor not solve polyaniline fiber intensity, the shortcoming that fragility is big, and its actual application is relatively poor, can not satisfy the demand of suitability for industrialized production.
Summary of the invention
One of technical issues that need to address of the present invention are to disclose a kind of polyaniline/polyacrylonitrile composite conducting fiber, to overcome the above-mentioned defective that prior art exists, satisfy the demand of suitability for industrialized production;
Two of the technical issues that need to address of the present invention provide the preparation method of above-mentioned polyaniline/polyacrylonitrile composite conducting fiber.
Technical conceive of the present invention is such: the inventor on the basis of existing technology, at first prepare the soluble polyaniline that organic sulfonic acid mixes, then with organic sulfonate and the polyacrylonitrile dissolving of mixed solvent with polyaniline, adopt the wet spinning technology that spinning solution was pressed spinning head then, clamp-on in the coagulating bath, make conductive fiber after drawn, the washing.
Polyaniline of the present invention/polyacrylonitrile conductive fiber is made up of the organic sulfonate and the polyacrylonitrile of conduction component polyaniline.
Wherein, be 1~40% in the content of the organic sulfonate of fibre weight polyaniline, the content of polyacrylonitrile is 60~99%;
The content of the organic sulfonate of preferred polyaniline is 5%~15%, and the content of polyacrylonitrile is 85~95%.
The organic sulfonate of said polyaniline is the polyaniline of organic sulfonic acid of having mixed, and wherein, the doping rate of organic sulfonic acid p-poly-phenyl amine is 30%~70%, (the doping rate is the mol ratio of element sulphur and nitrogen element).
Described polyaniline structure is as follows:
Wherein, y is between 0~1, and n is 8~1000;
The organic sulfonic acid of being addressed comprises camphorsulfonic acid or alkyl benzene sulphonate and derivative thereof.
Institute's alkyl benzene sulphonate of addressing and derivative molecular formula thereof are: RC
6H
5SO
3M, R=H, C
mH
M+1, m=2~15, M=H, Na, K.DBSA preferably;
The organic sulfonate of described polyaniline can be according to document " Electron diffraction studiesof the structure of polyaniline-dodecylbenzenesulfonate by Yang, C.Y.; Smith, P.; Heeger, A.J.; Cao, Y.; Osterholm, J.E.Polymer, 35 (1994) 1142-1147 and Solution characterization of surfactant solubilized polyaniline byGettinger, C.L.; Heeger, A.J.; Pine, D.J.; Cao, Y.Synthetic Metals, 74 (1995) 81-88 " disclosed method is prepared, and the present invention repeats no more.
The preparation method of polyaniline of the present invention/polyacrylonitrile conductive fiber comprises the steps:
(1) preparation of spinning solution: the organic sulfonate of polyaniline is dissolved in chloroform or/and in the dimethylbenzene, get solution A; Polyacrylonitrile is dissolved in dimethyl sulfoxide (DMSO) or/and in the dimethyl formamide, get solution B; With solution A and solution B mixed, obtain the co-blended spinning solution of polyaniline organic sulfonate and polyacrylonitrile according to the organic sulfonate and the polyacrylonitrile of above-mentioned polyaniline;
The organic sulfonate of polyaniline and the polyacrylonitrile weight percent concentration in mixed solvent is 10~40wt%.
(2) spinning: adopt conventional wet spinning process and equipment, it is that 40~60% dimethyl sulfoxide (DMSO) is or/and in the coagulating bath of the dimethyl formamide aqueous solution that above-mentioned spinning slurry is clamp-oned concentration by spinneret orifice, 10~30 ℃ of coagulation bath temperatures, making the pH value of coagulating bath with the organic sulfonic acid adjusting is 2~5, after high polymer solidifies, pass through deflector roll, in being 2~5 water, the pH value stretches, draw ratio is 4~8 times, adopt conventional method washing then, oil, drying promptly obtains polyaniline/polyacrylonitrile conductive fiber.
Does not wait in spinnerets hole count from 1 to 1000 hole used among the present invention, and the tow fineness of conductive fiber does not wait from 50dtex to 5000dtex.
The organic sulfonate of polyaniline can be according to document " Electron diffraction studies of thestructure of polyaniline-dodecylbenzenesulfonate by Yang, C.Y.; Smith, P.; Heeger, A.J.; Cao, Y.; Osterholm, J.E.Polymer, 35 (1994) 1142-1147 and Solution characterization of surfactant solubilized polyaniline by Gettinger, C.L.; Heeger, A.J.; Pine, D.J.; Cao, Y.Synthetic Metals, 74 (1995) 81-88 " disclosed method is prepared, or can be prepared according to following steps:
Method (1): with weight concentration is the aqueous solution that 10~30% ammonium persulfate (APS) aqueous solution adds DBSA (DBSA), aniline and chloroform, 0~20 ℃ was reacted 6~24 hours, from product, collect the polyaniline powder that DBSA mixes then, can preferably adopt following method to collect: in product, to add acetone, precipitation, filtration, water and acetone washing, 30~60 ℃ of dry polyaniline powders that get the DBSA doping.
Wherein: the aniline addition is 0.2~1%, and the ammonium persulfate addition is 0.2~0.6%, and the DBSA addition is 0.5~2%, and the chloroform addition is 0~40%, all is weight percentage (comprising water).
Method (2): with aniline concentration is 0.1~3mol/L, concentration of hydrochloric acid is that aniline salt acid solution and the ammonium persulfate concentration of 0.1~3mol/L is 1.5~3mol/L, concentration of hydrochloric acid is 0~10 ℃ of reaction of ammonium persulfate hydrochloric acid solution, 4~10h of 0.1~3mol/L, filter then, filter cake washes with hydrochloric acid solution, colourless until filtrate, filter cake is at 30~60 ℃ of following vacuumize 24~48h, obtain the polyaniline of doped hydrochloride, filter behind ammoniacal liquor immersion 10~30h with 10~30wt% again, filter cake is at 30~60 ℃ of following vacuumize 15~30h, the product that obtains and camphorsulfonic acid or DBSA are ground mixing by 1: 1~2.5 mol ratio, add the chloroform solvent, grind again, volatilization removes and desolvates, and promptly gets doping polyaniline powder, i.e. the organic sulfonate of polyaniline.
Polyaniline/polyacrylonitrile the conductive fiber that obtains with above-mentioned material and preparation method has excellent conducting performance, and electrical conductivity can be controlled in 10 because of the difference of polyaniline content in the fiber is different
-7-10
-1(S/cm) in the scope, the conductive fiber of the present invention's preparation has intensity preferably, generally at 1.5CN/dtex~3.4CN//dtex, can satisfy the instructions for use in weaving and other field substantially, except that can be used as semiconductor devices, electromagnetic shielding material and antistatic material, can also absorb radar, infrared ray, ultraviolet ray etc., be applied to many special dimensions.
The specific embodiment
Embodiment 1
The polyaniline dodecyl benzene sulfonate that takes by weighing 20 grams adds in the 180 gram chloroforms, stirs 6 hours at 40 ℃, gets solution A;
Again 180 gram polyacrylonitrile are added in the 600 gram dimethyl sulfoxide (DMSO)s, stirred 10 hours, get solution B at 60 ℃.Solution A is mixed with solution B, it was mixed in 6 hours, obtain co-blended spinning solution 50 ℃ of stirrings.
Adopt the wet spinning technology path, utilize conventional wet process equipment, above spinning slurry after filtration, behind the measuring pump, clamp-on in the coagulating bath by spinneret orifice, coagulating bath is the aqueous solution of dimethyl sulfoxide (DMSO), 20 ℃ of coagulation bath temperatures, the concentration of dimethyl sulfoxide (DMSO) are 50%, and adding a certain amount of DBSA, to make the pH value of coagulating bath be 3.After high polymer solidifies, by deflector roll, stretch in the pH value is 2 water, draw ratio is 6 times.Silk after the stretching enters rinsing machine.Fiber after the washing is after oil bath oils, and is dry in drying machine, reels afterwards.Promptly obtain polyaniline/polyacrylonitrile conductive fiber.The adulterant of this fiber is a DBSA, and blend solvent is chloroform/dimethyl sulfoxide (DMSO).The electrical conductivity of fiber is 0.26S/cm, and intensity is 1.98CN/dtex.
Embodiment 2
Repeat embodiment 1, following difference is arranged: take by weighing camsilate 15 grams of polyaniline, dissolve with 135 gram dimethylbenzene; Polyacrylonitrile 135 grams dissolve with 500 gram dimethyl sulfoxide (DMSO)s.The adulterant of this fiber is a camphorsulfonic acid, and blend solvent is dimethylbenzene/dimethyl sulfoxide (DMSO), and coagulating bath is 50% dimethyl sulphoxide aqueous solution.The electrical conductivity of fiber is 0.68S/cm, and intensity is 1.76CN/dtex.
Embodiment 3
Repeat embodiment 1, following difference is arranged: take by weighing dodecyl benzene sulfonate 10 grams of polyaniline, dissolve with 90 gram chloroforms; Polyacrylonitrile 190 grams are with 680 gram dmso solutions.The adulterant of this fiber is a DBSA, and blend solvent is chloroform/dimethyl sulfoxide (DMSO), and coagulating bath is 50% dimethyl sulphoxide aqueous solution.The electrical conductivity of fiber is 7.3 * 10
-3S/cm, intensity is 2.90CN/dtex.
Embodiment 4
Repeat embodiment 1, following difference is arranged: take by weighing dodecyl benzene sulfonate 10 grams of polyaniline, dissolve with 90 gram chloroforms; Polyacrylonitrile 190 grams are with 680 gram dimethyl formamide dissolvings.The adulterant of this fiber is a DBSA, and blend solvent is chloroform/dimethyl formamide, and coagulating bath is 50% the dimethyl formamide aqueous solution.The electrical conductivity of fiber is 5.6 * 10
-4S/cm, intensity is 3.03CN/dtex.
Embodiment 5
Repeat embodiment 1, following difference is arranged: take by weighing dodecyl benzene sulfonate 5 grams of polyaniline, dissolve with 45 gram dimethylbenzene; Polyacrylonitrile 195 grams are with 700 gram dmso solutions.The adulterant of this fiber is a DBSA, and blend solvent is dimethylbenzene/dimethyl sulfoxide (DMSO), and coagulating bath is 50% dimethyl sulphoxide aqueous solution.The electrical conductivity of fiber is 2.4 * 10
-6S/cm, intensity is 3.10CN/dtex.
Embodiment 6
Repeat embodiment 1, following difference is arranged: take by weighing camsilate 20 grams of polyaniline, dissolve with 180 gram dimethylbenzene; Polyacrylonitrile 110 grams dissolve with gram 440 dimethyl sulfoxide (DMSO)s.The adulterant of this fiber is a camphorsulfonic acid, and blend solvent is dimethylbenzene/dimethyl sulfoxide (DMSO), and coagulating bath is 50% dimethyl sulphoxide aqueous solution.The electrical conductivity of fiber is 0.98S/cm, and intensity is 1.50CN/dtex.
Claims (8)
1. polyaniline/polyacrylonitrile composite conducting fiber, it is characterized in that, organic sulfonate and polyacrylonitrile by polyaniline are formed, in fibre weight, the content of the organic sulfonate of polyaniline is 1~40%, the content of polyacrylonitrile is 60~99%, and said organic sulfonate is a neopelex.
2. polyaniline according to claim 1/polyacrylonitrile composite conducting fiber is characterized in that, the content of the organic sulfonate of polyaniline is 5%~15%, and polyacrylonitrile is 85~95%.
3. polyaniline according to claim 1/polyacrylonitrile composite conducting fiber is characterized in that, the organic sulfonate of said polyaniline is the polyaniline of organic sulfonic acid of having mixed, and the doping rate of organic sulfonic acid p-poly-phenyl amine is 30%~70%.
4. according to the preparation method of each described polyaniline/polyacrylonitrile composite conducting fiber of claim 1~3, it is characterized in that, comprise the steps:
(1) preparation of spinning solution: the organic sulfonate of polyaniline is dissolved in chloroform or/and in the dimethylbenzene, get solution A; Polyacrylonitrile is dissolved in dimethyl sulfoxide (DMSO) or/and in the dimethyl formamide, get solution B; With solution A and solution B mixed, obtain the co-blended spinning solution of polyaniline organic sulfonate and polyacrylonitrile according to above-mentioned polyaniline organic sulfonate and polyacrylonitrile;
(2) spinning: above-mentioned spinning slurry is clamp-oned dimethyl sulfoxide (DMSO) by spinneret orifice or/and in the coagulating bath of the dimethyl formamide aqueous solution, after high polymer solidifies, adopt conventional method to handle, promptly obtain polyaniline/polyacrylonitrile conductive fiber.
5. method according to claim 4 is characterized in that, the organic sulfonate of polyaniline and the polyacrylonitrile weight percent concentration in mixed solvent is 10~40wt%.
6. method according to claim 4 is characterized in that, dimethyl sulfoxide (DMSO) is or/and the weight percent concentration of the dimethyl formamide aqueous solution is 40~60%.
7. method according to claim 4 is characterized in that, coagulation bath temperature is 10~30 ℃.
8. according to each described method of claim 4~7, it is characterized in that the pH value of regulating coagulating bath with organic sulfonic acid is 2~5.
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CN1323199C (en) * | 2005-12-05 | 2007-06-27 | 西安交通大学 | Preparation method of conductive polymer polyanilinc nano fiber |
CN101967279B (en) * | 2010-09-25 | 2012-09-05 | 东华大学 | Method for preparing reversible discolouring membrane made from polyaniline composite nanofiber |
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CN103556299A (en) * | 2013-10-30 | 2014-02-05 | 苏州龙杰特种纤维股份有限公司 | Polyaniline/polyacrylonitrile elastic composite conductive fiber and preparation method thereof |
CN103668502A (en) * | 2013-12-19 | 2014-03-26 | 吴江明敏制衣有限公司松陵分公司 | Ultra-fine sheath-core yarn wire |
CN105177758A (en) * | 2015-10-26 | 2015-12-23 | 太仓市双宇化纤有限公司 | Antistatic polyacrylonitrile/polyaniline composite fiber material and preparation method thereof |
CN105624824B (en) * | 2016-01-29 | 2018-01-05 | 苏州大学 | A kind of preparation method of Conductive Polyaniline Fibers |
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CN115360528B (en) * | 2022-10-24 | 2022-12-30 | 中国科学院长春光学精密机械与物理研究所 | Radar switch frequency selective surface loaded with polyaniline |
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