CN1760242A - Wave absorption material containing polyaniline, manufacturing method and equipment - Google Patents
Wave absorption material containing polyaniline, manufacturing method and equipment Download PDFInfo
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- CN1760242A CN1760242A CN 200510057368 CN200510057368A CN1760242A CN 1760242 A CN1760242 A CN 1760242A CN 200510057368 CN200510057368 CN 200510057368 CN 200510057368 A CN200510057368 A CN 200510057368A CN 1760242 A CN1760242 A CN 1760242A
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Abstract
A wave absorbing material containing polyphenylamine is a composite polyphenylamine-polytetrafluoro ethene (Pan-PEFE) film. Its preparing process includes such steps as provide polytetrafluoro ethene film as substrate, washing, immersing it in a monomer solution, clamping the substrate by two glass bathes respectively containing phenylamine solution and oxidant solution, and polymerizing reaction in the arteries and on the surface of substrate. Its apparatus is also disclosed.
Description
Technical field
The present invention relates to absorb electromagnetic material, relate in particular to the polymer absorbing material of absorbing radar wave.
Background technology
The absorbing material of radar wave is a material with fastest developing speed in the stealth material, most widely used, is subjected to the great attention of countries in the world always.No matter be structure-type wave-absorption material or coating type absorbing material, all need to add the absorbing material that hertzian wave is had sorption, the wave-absorbing effect of the performance decision whole object of absorbing material.Therefore, absorbing material is the core technology in the Radar Stealth Materials.
The material obsorbing radar waves kind is a lot, but still has many shortcomings in actual applications.At present, the exploitation that has the novel wave-absorbing material of " thin, wide, light " characteristics has become the focus of research.
The conducting polymer absorbing material has advantages such as in light weight, that mechanical property is superior, The Nomenclature Composition and Structure of Complexes is easy to control, demonstrates very strong design flexibility in the absorbing radar wave frequency range.The conducting polymer absorbing material is the recent studies on field of conducting polymer and absorbing material subject crossing.Organic conductive macromolecule has the πDian Zi conjugated system, after mixing, there is free radical on its chain structure, the existence of this class dipole and transition make it have electroconductibility, its specific conductivity changes in isolator, semi-conductor and range of metal, different specific conductivity presents different absorbing properties, carry out charge transfer by chemistry or electrochemical method and doping agent and be used for designing its conductive structure, capable of realizing impedance matching and electromagnetic consumable, thereby absorbing radar wave.
The conducting polymer absorbing material mainly comprises polyphenylacetylene, polypyrrole, Polythiophene, polyaniline, polyphenylene sulfide etc.Because they have structure diversity, and unique physics, chemical property, and density is little, and machining property is good, middle low-temperature stability height, thereby the person of being studied extensively payes attention to.In numerous conducting high polymers things, polyaniline (PAn) cost of material is cheap, synthetic simply, conductivity is good, therefore is subjected to special attention; In the absorbing material field, polyaniline has broad application prospects.But because strong effect and high stiff chain between polyaniline molecule, the doped polyaniline that is in conductive state is dissolved in any solvent hardly, and comprehensive mechanical property is relatively poor, can't process with the traditional method straight forming, and this has limited its application to a great extent.
Summary of the invention
First purpose of the present invention is, the deficiency at prior art exists provides a kind of comprehensive mechanical property good, can be with the absorbing material that contains polyaniline of traditional method straight forming processing;
Second purpose of the present invention is that a kind of described method that contains the absorbing material of polyaniline of making is provided;
The 3rd purpose of the present invention is that a kind of described device that contains the absorbing material of polyaniline of making is provided.
What realize the present invention's first purpose is a kind of like this absorbing material that contains polyaniline: same as the prior art, the contained polyaniline (PAn) of this material also is the conductive structure that doping agent is arranged; What be different from prior art is that this absorbing material that contains polyaniline is polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane.Polytetrafluoroethylene (PTFE) wherein is a basement membrane, polyaniline (PAn) be by aniline penetrate in the microchannel of this basement membrane and in the film surface, with the composite bed that this basement membrane is compounded to form, this polyaniline (PAn) is of a size of nano level in the basement membrane microchannel.That is to say, absorbing radar wave be to be compounded in to be the polyaniline of conductive structure (PAn) on the polytetrafluoroethylene (PTFE) basement membrane, the polytetrafluoroethylene (PTFE) basement membrane be improve the comprehensive mechanical property of polyaniline (PAn) and workability can carrier (or perhaps flexible back bone).
What realize the present invention's second purpose is a kind of like this method, and this method comprises the steps:
A. clean the polytetrafluoroethylene (PTFE) basement membrane with organic solvent, so that the greasy dirt in membrane surface and the microchannel is removed;
B. soak into basement membrane with organic solvent, place the monomer solution that contains aniline to soak then 10~20 hours;
C. will place the center fixed of a bathing pool device through the polytetrafluoroethylene (PTFE) basement membrane that soaks; One side of the polytetrafluoroethylene (PTFE) basement membrane in this bathing pool device is packed into and is participated in the monomer solution that contains aniline of polyreaction, and its opposite side is packed into and participated in the oxidizing agent solution of polyreaction; Make by diffusion to be placed in the aniline of polytetrafluoroethylene (PTFE) basement membrane both sides and oxygenant, in the microchannel of basement membrane He in the film surface, carry out polyreaction, with formation polyaniline (PAn) alternatively by the microchannel of basement membrane;
D. after polyreaction finishes, polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane that makes is also dried with distilled water wash, p-poly-phenyl amine (PAn) mixed 20~30 hours in advance then, and secondary doping is 40~60 hours behind the repetitive scrubbing;
E. polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane after mixing with distilled water wash is clean, last vacuum-drying.
What realize the present invention's the 3rd purpose is a kind of like this device, and this device is the bathing pool device that is applied in the aforementioned polyreaction.This bathing pool device comprises two symmetric glass half bathing pools that are linked together by unit bolt nut, two joining a pair of pool walls of glass half bathing pool are AND DEWATERING FOR ORIFICE STRUCTURE, are attached with each one eyelet on it and the corresponding silica-gel plate of eyelet on the orifice plate in the outside of each orifice plate; Place bathing pool device intermediary polytetrafluoroethylene (PTFE) basement membrane to be clamped in regularly between these two blocks of silica-gel plates, the monomer solution that contains aniline is contained in glass half bathing pool, and oxidizing agent solution is contained in another glass half bathing pool.
Superiority of the present invention is as follows:
Compare with the existing doped polyaniline that is in conductive state, owing to be organic polymer material [tetrafluoroethylene (PTFE)] and the compound conductive composite film material that contains polyaniline that manufactures of polyaniline with good mechanical properties, therefore, improve the comprehensive mechanical property of polyaniline widely, can process the absorbing material that contains polyaniline of the present invention with traditional processing composite membrane way fully.
Obviously, after the present invention disclosed out polyaniline/tetrafluoroethylene (PAn/PTFE) composite wave-absorbing film, those skilled in the art will produce this composite membrane, is not difficult.The scheme of realization second goal of the invention that this case discloses is that a kind of film permeates situ aggregation method mutually.The reaction conditions gentleness of this method, recombination process are easy to control, can realize the variation of composite membrane function.The scheme of realization the 3rd goal of the invention that this case discloses has been created condition for using this film to permeate situ aggregation method mutually reliably, makes this recombination process be more prone to (according to the different specific conductivity of required composite membrane) control, yield rate height.
In a word, the present invention is that wide prospect has been opened up in the application of polyaniline (PAn) raw material aspect absorbing material.
The present invention is further illustrated below in conjunction with drawings and Examples.
Description of drawings
Fig. 1---bathing pool schematic representation of apparatus of the present invention.
Fig. 2---under the 3mm wave band, the reflectivity of the PAn/PTFE composite membrane of different specific conductivity.
Embodiment
A kind of absorbing material that contains polyaniline, polyaniline wherein (PAn) is for there being the conductive structure of doping agent.This absorbing material that contains polyaniline is polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane.Polytetrafluoroethylene (PTFE) in this composite membrane is a basement membrane 1, polyaniline (PAn) penetrate in this basement membrane 1 (just has poly tetrafluoroethylene) microchannel itself by aniline and the film surface in, and the composite bed that is compounded to form of this basement membrane 1, this polyaniline (PAn) is of a size of nano level (the nano level here in basement membrane 1 microchannel, be the result who just has naturally after the polyreaction, the duct size of basement membrane has restriction to the size of polymeric polyaniline in the fenestra).In view of after those skilled in the art seen that literal discloses, can understand the structure of this composite membrane fully, so do not draw accompanying drawing.
In a kind of procedure of manufacturing above-mentioned polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane, carry out the bathing pool device (this manufacture method is in an embodiment again further combined with the processing condition introduction) of polyreaction.This bathing pool device comprises that 3, two glass of two symmetric glass half bathing pools, half bathing pool, the 3 joining a pair of pool walls that are linked together by unit bolt nut 4 are orifice plate 31 structures; Be attached with the corresponding silica-gel plate 2 of eyelet 231 on each one eyelet 231 on it and the orifice plate 31 in the outside of each orifice plate 31.Place bathing pool device intermediary polytetrafluoroethylene (PTFE) basement membrane 1 to be clamped in regularly between these two blocks of silica-gel plates 2, the monomer solution 5 that contains aniline is contained in a glass half bathing pool 3, and oxidizing agent solution 6 is contained in another glass half bathing pool 3.Obviously, eyelet 231 sizes on said pool wall and the silica-gel plate 2, quantity be with guarantee polyreaction can be normally, carry out apace, can guarantee polytetrafluoroethylene (PTFE) basement membrane 1 degree of being retained as that is fixed reliably again.
Above-mentioned embodiment is following each routine summation, so content same as described above is not given unnecessary details in following each example.
Embodiment 1:
This part is with ammonium persulphate [(NH
4)
2S
4O
8] make an example of polyaniline/tetrafluoroethylene (PAn/PTFE) conductive composite film for oxygenant.Concrete steps are as follows:
A. cut out polytetrafluoroethylene (PTFE) film, the polytetrafluoroethylene (PTFE) basement membrane 1 that cuts is put into organic solvent ethanol or acetone (this example is ethanol), to carry out ultrasonic cleaning as basement membrane 1.Scavenging period and clean level can normally carry out degree of being to guarantee follow-up polyreaction.
B. the polytetrafluoroethylene (PTFE) basement membrane 1 that cleans up is put into clean ethanol and soaks into, forward monomer solution again to---soak in aniline/hydrochloric acid soln.Soak time is 18 hours;
C. polytetrafluoroethylene (PTFE) basement membrane 1 fixed clamp of soaking between the silica-gel plate 2 on two glass, half bathing pool 3 of bathing pool device (with reference to figure 1), in a glass half bathing pool 3, add aniline/hydrochloric acid monomer solution, in another glass half bathing pool 3, add oxygenant ammonium persulphate [(NH
4)
2S
4O
8]---to carry out polyreaction.That is: make by diffusion and be placed in the aniline of polytetrafluoroethylene (PTFE) basement membrane 1 both sides and oxygenant, in the microchannel of basement membrane 1 He in the film surface, carry out polyreaction, with formation polyaniline (PAn) alternatively by the microchannel of basement membrane 1.Concrete processing condition are as follows:
Aniline and (NH
4)
2S
2O
8Mol ratio: 1.0;
Concentration of hydrochloric acid: 2.0molL
-1
Temperature of reaction: 5 ℃;
Polymerization time: 2.5h.
D. polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane that makes is also dried with distilled water wash, p-poly-phenyl amine (PAn) mixed 28 hours in advance then, and pre-adulterated reagent is strong aqua; Secondary doping is 55 hours behind the repetitive scrubbing, and the reagent of secondary doping is hydrochloric acid soln;
E. polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane after mixing with distilled water wash is clean, last vacuum-drying.
The maximum surface conductivity and the section specific conductivity of gained composite membrane are respectively 3.07scm
-1With 1.07 * 10
-5Scm
-1
Embodiment 2:
The manufacture method of this example and process are identical with embodiment's 1, and same section is not given unnecessary details.Different aspects is (among the step c) polymerization technology condition difference, and these routine processing condition are:
Aniline and (NH
4)
2S
2O
8Mol ratio: 0.5;
Concentration of hydrochloric acid: 1.0molL
-1
Temperature of reaction: 0 ℃;
Polymerization time: 5h.
The maximum surface conductivity and the section specific conductivity of gained composite membrane are respectively 3.14scm
-1With 1.02 * 10
-4Scm
-1
Embodiment 3:
The manufacture method of this example and process are identical with embodiment's 1, and same section is not given unnecessary details.Different aspects is (among the step c) polymerization technology condition difference, and these routine processing condition are:
Aniline and (NH
4)
2S
2O
8Mol ratio: 4.0;
Concentration of hydrochloric acid: 5.0molL
-1
Temperature of reaction: 20 ℃;
Polymerization time: 5h.
The maximum surface conductivity and the section specific conductivity of gained composite membrane are respectively 2.87scm
-1With 0.94 * 10
-5Scm
-1
Embodiment 4:
The manufacture method of this example and process are identical with embodiment's 1, and same section is not given unnecessary details.Different aspects are that this part is with sodium vanadate (Na
3VO
4) make an example of polyaniline/tetrafluoroethylene (PAn/PTFE) conductive composite film for oxygenant.With embodiment 1 different aspect be:
When a. the polytetrafluoroethylene (PTFE) basement membrane 1 that cuts being carried out ultrasonic cleaning, put into organic solvent-acetone;
B. the polytetrafluoroethylene (PTFE) basement membrane 1 that soaked into is put into monomer solution---the time that aniline/hydrochloric acid soln soaks is 16 hours;
C. different processing condition are as follows in the polyreaction:
Aniline/Na
3VO
4Monomer concentration ratio: 1/1;
Concentration of hydrochloric acid: 2.0molL
-1
Range of reaction temperature: 10 ℃;
Reaction time range: 150min.
D. the pre-doping time of p-poly-phenyl amine (PAn) is 25 hours, and the secondary doping time is 50 hours;
The section specific conductivity of gained composite membrane brings up to 2.31 * 10
-3Scm
-1, surface conductivity slightly reduces, and is 2.62scm
-1
Embodiment 5:
The manufacture method of this example and process are identical with embodiment's 1, and same section is not given unnecessary details.Different aspects are that this part is with iron trichloride (FeCl
3) make an example of polyaniline/tetrafluoroethylene (PAn/PTFE) conductive composite film for oxygenant.With embodiment 1 different aspect be:
B. the polytetrafluoroethylene (PTFE) basement membrane 1 that soaked into is put into monomer solution---the time that aniline/hydrochloric acid soln soaks is 12 hours;
C. different processing condition are as follows in the polyreaction:
Aniline/FeCl
3Monomer concentration ratio: 1/2;
Concentration of hydrochloric acid: 1molL
-1
Temperature of reaction: 60 ℃;
Reaction times: 24h.
D. the pre-doping time of p-poly-phenyl amine (PAn) is 22 hours, and the secondary doping time is 45 hours;
The surface conductivity and the section specific conductivity of the PAn/PTFE conductive composite film of gained composite membrane are respectively 0.355scm
-1With 8.23 * 10
-5Scm
-1
Obviously, each composite membrane of each routine manufacture method and correspondence thereof and non exhaustive more than.Conducting high polymers thing polyaniline (PAn) has special advantages as a kind of novel wave-absorbing material aspect radar-wave absorbing.By experiment, studied the manufacturing process of this polyaniline/tetrafluoroethylene (PAn/PTFE) composite wave-absorbing film, and the relation of specific conductivity and radar-wave absorbing performance, and the research by this relation, inquired into the wave-absorbing mechanism of polyaniline, searched out a kind of novel wave-absorbing material (with reference to figure 2, the corresponding respectively surface conductivity of representing embodiment 1,2 and 3 of the two dot chain line in Fig. 2, solid line and dotted line) that has good absorbing property at the 3mm wave band.
Owing in the manufacturing processed of this composite membrane, generated the polyaniline of some nano-scales in the fenestra of basement membrane 1PTFE, make composite membrane under the few situation of polyaniline content, still have certain microwave absorbing property.
Microwave absorbing property is relevant with conductivity of electrolyte materials, and along with the raising of specific conductivity, absorbing property obviously improves.Because polyaniline has the πDian Zi conjugated system, there is free radical on the molecular chain structure, when radar wave shines material surperficial, if material impedance matching, hertzian wave will enter the inside of material, and at this moment, the dipole of polyaniline inside is subjected to the electromagnetic influence of corresponding frequencies and transition takes place, thereby by interelectric interaction microwave energy is converted into heat energy, realizes absorption microwave.In the polyaniline of good conductivity, the restraint force of molecular chain length and molecular structure electrode couple is little than the bad polyaniline of electroconductibility, is easier to microwave energy is converted to heat energy, thereby improves absorbing property.
Claims (5)
1, the absorbing material that contains polyaniline, polyaniline wherein (PAn) is characterized in that for the conductive structure of doping agent is arranged this absorbing material that contains polyaniline is polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane; Polytetrafluoroethylene (PTFE) wherein is basement membrane (1), polyaniline (PAn) be by aniline penetrate in the microchannel of this basement membrane (1) and in the film surface, and the composite bed that is compounded to form of this basement membrane (1), this polyaniline (PAn) is of a size of nano level in basement membrane (1) microchannel.
2, make the method for polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane, it is characterized in that this method comprises the steps:
A. clean polytetrafluoroethylene (PTFE) basement membrane (1) with organic solvent, so that the greasy dirt in basement membrane (1) surface and the microchannel is removed;
B. soak into basement membrane (1) with organic solvent, place the monomer solution (5) that contains aniline to soak then 10~20 hours;
C. will place the center fixed of a bathing pool device through the polytetrafluoroethylene (PTFE) basement membrane (1) that soaks; The oxidizing agent solution (6) that the monomer solution that contains aniline (5) that one side of the polytetrafluoroethylene (PTFE) basement membrane (1) in this bathing pool device is packed into and participated in polyreaction, its opposite side are packed into and participated in polyreaction; Make by diffusion to be placed in the aniline of polytetrafluoroethylene (PTFE) basement membrane (1) both sides and oxygenant, in the microchannel of basement membrane (1) He in the film surface, carry out polyreaction, with formation polyaniline (PAn) alternatively by the microchannel of basement membrane (1);
D. after polyreaction finishes, polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane that makes is also dried with distilled water wash, p-poly-phenyl amine (PAn) mixed 20~30 hours in advance then, and secondary doping is 40~60 hours behind the repetitive scrubbing;
E. polyaniline/tetrafluoroethylene (PAn/PTFE) composite membrane after mixing with distilled water wash is clean, last vacuum-drying.
3, the method for manufacturing polyaniline/tetrafluoroethylene according to claim 2 (PAn/PTFE) composite membrane is characterized in that:
The organic solvent that cleans polytetrafluoroethylene (PTFE) basement membrane (1) in step a is ethanol or acetone, and its method is polytetrafluoroethylene (PTFE) basement membrane (1) to be placed on carry out ultrasonic cleaning in ethanol or the acetone;
The organic solvent that soaks into basement membrane (1) in step b is an ethanol, and the monomer solution that soaks basement membrane (1) is aniline/hydrochloric acid soln;
The monomer solution of packing in step c is aniline/hydrochloric acid soln, and oxygenant is ammonium persulphate [(NH in the oxidizing agent solution of packing into (6)
4)
2S
4O
8], sodium vanadate (Na
3VO
4) or iron trichloride (FeCl
3);
Pre-adulterated reagent is strong aqua in steps d, and the reagent of secondary doping is hydrochloric acid soln.
4, the method for manufacturing polyaniline/tetrafluoroethylene according to claim 3 (PAn/PTFE) composite membrane is characterized in that: oxygenant is ammonium persulphate [(NH in the oxidizing agent solution of packing in step c (6)
4)
2S
4O
8]; The processing condition of this polyreaction are:
Aniline and (NH
4)
2S
2O
8Mol ratio: 0.5~4.0;
Concentration of hydrochloric acid: 1~5molL
-1
Temperature of reaction: 0~20 ℃;
Polymerization time: 2.5~5h.
5, according to the method for claim 2,3 or 4 described manufacturing polyaniline/tetrafluoroethylene (PAn/PTFE) composite membranes, it is characterized in that: in the polyreaction of step c, described bathing pool device comprises two symmetric glass half bathing pools (3) that are linked together by unit bolt nut (4), the joining a pair of pool wall of two glass half bathing pools (3) is orifice plate (31) structure, is attached with each one eyelet (231) on it and the corresponding silica-gel plate (2) of eyelet (231) on the orifice plate (31) in the outside of each orifice plate (31); The described bathing pool device intermediary polytetrafluoroethylene (PTFE) basement membrane (1) that places is clamped between these two blocks of silica-gel plates (2) regularly, the described monomer solution (5) that contains aniline is contained in glass half bathing pool (3), and described oxidizing agent solution (6) is contained in another glass half bathing pool (3).
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101225178B (en) * | 2007-12-24 | 2011-04-06 | 天津大学 | Method for preparing polyaniline conductive composite film by in-situ polymerization |
CN111229050A (en) * | 2020-01-21 | 2020-06-05 | 吕剑阳 | Preparation method of composite membrane |
CN114243070A (en) * | 2021-12-15 | 2022-03-25 | 中国科学院大连化学物理研究所 | Proton exchange composite membrane of coupling conductive macromolecule and preparation method |
Family Cites Families (2)
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JPH02730A (en) * | 1988-01-29 | 1990-01-05 | Nippon Seirou Kk | Production of ester |
CN1101161A (en) * | 1993-09-30 | 1995-04-05 | 中国科学院化学研究所 | conductive polymer composite film and preparation method |
-
2005
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101225178B (en) * | 2007-12-24 | 2011-04-06 | 天津大学 | Method for preparing polyaniline conductive composite film by in-situ polymerization |
CN111229050A (en) * | 2020-01-21 | 2020-06-05 | 吕剑阳 | Preparation method of composite membrane |
CN111229050B (en) * | 2020-01-21 | 2022-02-18 | 吕剑阳 | Preparation method of composite membrane |
CN114243070A (en) * | 2021-12-15 | 2022-03-25 | 中国科学院大连化学物理研究所 | Proton exchange composite membrane of coupling conductive macromolecule and preparation method |
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