CN1202163C - Supercritical CO2 process of preparing conductive composite polypyrrole film material - Google Patents
Supercritical CO2 process of preparing conductive composite polypyrrole film material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 15
- 239000000463 material Substances 0.000 title claims description 3
- 230000008569 process Effects 0.000 title description 2
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- 239000000178 monomer Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000012530 fluid Substances 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 25
- 229920001940 conductive polymer Polymers 0.000 claims description 24
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 239000004793 Polystyrene Chemical class 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 claims description 8
- 229920002223 polystyrene Chemical class 0.000 claims description 8
- 229920001467 poly(styrenesulfonates) Chemical class 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 229920000181 Ethylene propylene rubber Chemical class 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- JRSGPUNYCADJCW-UHFFFAOYSA-K iron(3+);trichlorate Chemical group [Fe+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O JRSGPUNYCADJCW-UHFFFAOYSA-K 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229940032296 ferric chloride Drugs 0.000 claims 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 239000012466 permeate Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000012429 reaction media Substances 0.000 abstract description 5
- 230000002522 swelling effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 229910052785 arsenic Inorganic materials 0.000 description 8
- 239000002322 conducting polymer Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 229920002943 EPDM rubber Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 206010011224 Cough Diseases 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001562081 Ikeda Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000005442 molecular electronic Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明提供了一种新的聚吡咯导电复合膜的制备方法：利用超临界流体CO2对聚合物基体较强的溶胀性，将溶解在超临界CO2中的吡咯单体带入含有氧化剂的基体膜中引发聚合，生成导电聚吡咯复合膜。控制反应条件可得到仅表面导电或体积导电的聚吡咯复合膜。与已有的文献、专利相比，本发明采用无毒、不可燃的超临界CO2作为反应介质，省去了水或其他一些有毒溶剂如甲醇、乙腈的使用，因而具有环保特性，是一种非常有应用前景的导电复合材料制备技术。The invention provides a new preparation method of polypyrrole conductive composite film: using the strong swelling property of supercritical fluid CO2 on the polymer matrix, the pyrrole monomer dissolved in supercritical CO2 is brought into the atmosphere containing oxidant Polymerization is initiated in the matrix film to generate a conductive polypyrrole composite film. The polypyrrole composite film with only surface conduction or volume conduction can be obtained by controlling the reaction conditions. Compared with the existing documents and patents, the present invention uses non-toxic and non-flammable supercritical CO2 as the reaction medium, eliminating the use of water or other toxic solvents such as methanol and acetonitrile, so it has environmental protection characteristics and is a A very promising technology for the preparation of conductive composite materials.
Description
Invention field
The invention relates to a kind of method of utilizing supercritical fluid technology to prepare the polypyrrole conductive composite film.
Technical background
Successfully to have synthesized specific conductivity first be 1.7 * 10 since the Ikeda of Japan in 1971 and Shriakawa
9Scm
-1(cis), 4.4 * 10
-5Scm
-1Since (trans) polyacetylene film, the research of synthetic method, performance and the application prospect of intrinsically conducting polymer has been caused the very big attention of scientific circles.With the metallographic phase ratio, the density of conductive polymers is little, conductivity range wide (10
-7Scm
-1-10
4Scm
-1), have unique physicochemical property again concurrently.As the optical absorption characteristics under reversible redox characteristic, the different state of oxidation, electric look etc., thereby have broad application prospects at aspects such as secondary cell, molecular electronic device, electromagnetic shielding, biological or chemical transmitter, anti-corrosion of metal.
That polypyrrole has is easily synthetic, Heat stability is good, higher advantages such as specific conductivity, is the research emphasis in the present conducting polymer field.Yet, be not that black powder is exactly the film that overlays on electrode surface according to the polypyrrole of traditional method preparation.In addition, because the big conjugated in the linear molecule chain makes it have extremely strong rigidity, polypyrrole can not dissolve in fusion yet, and this makes it be difficult to machine-shaping, the also non-constant of mechanical property, thereby up to the present only realized commercialization in very limited field.One of effective means that overcomes the above-mentioned shortcoming of polypyrrole is that itself and macromolecule resin is compound, preparation polypyrrole conducing composite material.By appropriate selection, can make this matrix material have excellent conducting performance and mechanical property simultaneously.
In on January 5th, 1999 laid-open U.S. Patents 5855819, people such as DeSimone are by introducing supercritical CO with conductive polymers monomer and oxygenant
2, at the supercritical CO of certain temperature and pressure
2Middle polymerization generates conductive polymers.But this technology only relates at supercritical CO
2Synthesizing of middle body conductive polymers, do not relate to and utilize supercritical fluid technology to prepare conducting polymer composite material.
1986, the patent of invention CN861013891 of application such as Qian Renyuan, its technical characterictic is to make the monomer molecule of conductive polymers infiltrate through the flexible-chain polymer matrix by solvent-swollen earlier, makes monomer original place polymeric method in matrix prepare conductive composite film again under the effect of ionogen (oxygenant).In on December 5th, 2000 laid-open U.S. Patents 6,156,235, people such as Weiss make it can be dissolved in supercritical CO the oxygenant modification
2, and utilize supercritical CO
2Swelling action bring matrix polymer into.Then, the matrix polymer that will have oxygenant immerses in the monomeric solution of conductive polymers, and polymerization obtains conductive composite film.But all relating to, above-mentioned patent do not utilize supercritical CO
2The conductive polymers monomer is brought in the matrix polymer that is mixed with oxygenant, and then, polymerization obtains conducting polymer composite material.And aforesaid method all is dissolved with the influence of the monomeric solvent of conductive polymers to the matrix polymer swelling property, and conductive polymers can only infiltrate the degree of depth of tens microns of matrix polymers, thereby the conductive composite film of preparation all can only surface conduction.
Summary of the invention
The objective of the invention is to utilize supercritical CO
2Technology provides a kind of novel method for preparing the polypyrrole conductive composite film, and then researches and develops the conducting polymer composite membrane with actual application prospect.
Preparation polypyrrole conductive composite film method of the present invention, its conductive polymers monomer is pyrrole monomer (Pyrrole), utilizes supercritical CO
2Technology is brought monomer in the matrix polymer that is mixed with oxygenant in advance, then at supercritical CO
2Initiated polymerization under the condition, the poly-arsenic of preparation is coughed up conductive composite film.
One of technical characterictic of the present invention is the selection of reaction medium.At first, it must have good swelling property to polymeric matrix, simultaneously monomer is had certain dissolving power.Like this, by means of the swelling of reaction medium to the matrix that is mixed with oxygenant in advance, the monomer infiltration that is dissolved in the medium is gone into matrix inside, runs into oxygenant and polymerization takes place in situ generates conducting polymer composite material.The reaction medium of Xuan Zeing is a supercritical CO in the present invention
2, the conductive polymers monomer can penetrate into polymerization reaction take place in the matrix polymer fully, thereby can obtain only surface conduction or surface and inner all composite membranes of conduction by controlling reaction time.Be different from existing situ aggregation method and prepare conducting polymer composite material, the present invention has avoided in polymerization process water or some other deleterious organic solvent such as methyl alcohol, acetonitrile etc. as reaction medium.And supercritical CO
2Nontoxic, not flammable, thereby have environmental protection characteristic.
Two of technical characterictic of the present invention is to select for use non-polycrystalline macromolecule as matrix polymer, as: the amorphous high molecular polymers such as zinc salt of polycarbonate (PC), amorphous polyethylene terephthalate (APET), polymethylmethacrylate (PMMA), polyvinyl chloride (PVC), ethylene-propylene rubber(EPR) (EPDM), polystyrene (PS) or sulfonated polystyrene.
Three of technical characterictic of the present invention is that used oxygenant can be ferric chlorate, FERRIC CHLORIDE ANHYDROUS, Iron(III) chloride hexahydrate, iron nitrate, cupric chloride or its mixture.In the present invention, through peroxidation, radical cation coupling, processes such as deprotonation generate electric polypyrrole to pyrrole monomer under the effect of oxygenant.Oxygenant plays the effect of doping agent simultaneously, and doping attitude polypyrrole can exceed several magnitude than unadulterated polypyrrole on specific conductivity.For keeping electric neutrality, as counter ion negatively charged ion is directly provided by oxygenant.And with the difference to anionic nature, the specific conductivity of conductive polymers can change in the scope of broad.Therefore, can adopt different oxygenants to have the conducting polymer composite material of different conductivities with preparation.
Four of technical characterictic of the present invention is choice of Solvent, can be 1,2-ethylene dichloride, trichloromethane, tetrahydrofuran (THF), toluene or its mixed solvent.Because polyreaction is to take place run into oxygenant in monomer diffuses into matrix after, thereby require the oxygenant should be at the inner homodisperse of matrix, so that conductive polymers homodisperse in matrix.In the present invention, requirement to solvent is: a certain solvent can dissolve matrix polymer and oxygenant simultaneously, or two kinds of solvents can dissolve matrix polymer and oxygenant respectively, and these two kinds of solvents can dissolve each other, then polymer-based carbon liquid solution and oxidizing agent solution are mixed, spread film, to solve the homodisperse problem of oxygenant.
It is proceed step by step in the following order that the poly-arsenic of preparation of the present invention is coughed up the conductive composite film method:
(1) oxygenant and matrix polymer are dissolved in respectively in the appropriate solvent by weight 5/95～50/50, with behind the two uniform mixing at sheet glass upper berth film.After treating that solvent volatilizees substantially, transfer to that vacuum-drying obtained the matrix polymer film that is mixed with oxygenant of 0.1～1 mm thick thoroughly to remove clean solvent in 48 hours in 40 ℃ the baking oven.
The solvent of above-mentioned dissolved oxygen thing and matrix polymer can be ethylene dichloride, trichloromethane, tetrahydrofuran (THF) or its mixed solvent.Matrix can be the amorphous high molecular polymers such as zinc salt of polycarbonate (PC), amorphous polyethylene terephthalate (APET), polymethylmethacrylate (PMMA), polyvinyl chloride (PVC), ethylene-propylene rubber(EPR) (EPDM), polystyrene (PS) or sulfonated polystyrene.
(2) step (1) gained is mixed with the matrix polymer film of oxygenant and arsenic and coughs up monomer and place autoclave, feed 99.9% high-purity CO
2, condition is controlled to be: 33～100 ℃ of temperature, pressure 8～30MPa make CO
2Reach supercritical state, constant temperature and pressure 20 minutes～24 hours makes the conductive polymers monomer be penetrated in the matrix polymer with supercutical fluid and finishes polyreaction.
(3) in 10～60 second time, communicated, obtain poly-arsenic and cough up conductive composite film with supercutical fluid release and with atmosphere.
(4) with the polypyrrole conductive composite film that obtains with deionized water, methyl alcohol repetitive scrubbing for several times to remove unreacted oxidant and by product in the striping.
Method for preparing a kind of poly-arsenic cough up conductive composite film, its thickness is 0.1～1 millimeter, its surface and inner conductivity value are 10
-6To 10
0Scm
-1Between.After polymerization finished, the surface of matrix polymer film and transverse section can all become black by yellow, and this explanation arsenic is coughed up monomer and can be infiltrated base film inside fully and polymerization takes place.And polypyrrole/matrix composite membrane is immersed in the solvent again, can not be dissolved only can be by swelling, this explanation has formed the network structure of polypyrrole in composite membrane.Just because of above-mentioned cancellated existence, even if when very low poly-arsenic is coughed up content, composite membrane can reach higher specific conductivity.Above-mentioned poly-arsenic is coughed up the specific conductivity of conductive composite film and is measured with the standard four probe method.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention and effect are further described.But employed concrete grammar, prescription and explanation are not limitation of the present invention.
Embodiment 1:
Earlier the 0.8g FERRIC CHLORIDE ANHYDROUS is dissolved in 20ml 1, in the 2-ethylene dichloride, 2g polystyrene (Yanshan Petrochemical is in advance in 80 ℃ of following vacuum oven 24 hours) is dissolved in 10ml 1, the 2-ethylene dichloride, with the two uniform mixing, be mixed with the solution that oxidant concentration is 40% (weight ratio) again.Solution is poured on the sheet glass, treats to transfer to 40 ℃ of vacuum oven 48 hours after solvent volatilizees to the greatest extent substantially, obtain the Polystyrene Film that is mixed with the oxygenant iron trichloride that thickness is about 0.48 millimeter.
The film for preparing is put into autoclave simultaneously with new distillatory pyrrole monomer, and temperature is 40 ℃, and pressure is 15MPa, reacts 12 hours.After reaction finished, Polystyrene Film became black by original Vandyke brown, and specific conductivity is 1.15 * 10
-6S/cm.
Embodiment 2:
Earlier the 2g FERRIC CHLORIDE ANHYDROUS is dissolved in 40ml 1, in the 2-ethylene dichloride, the 2g polystyrene is dissolved in 10ml 1, the 2-ethylene dichloride, again with the two uniform mixing, is mixed with the solution that oxidant concentration is 100% (weight ratio).The step of all the other preparation films and reactions steps are with embodiment 1.After reaction finished, Polystyrene Film became black by original Vandyke brown, and specific conductivity is 2.07 * 10
-6S/cm.
Embodiment 3:
Earlier the 0.8g FERRIC CHLORIDE ANHYDROUS is dissolved in the 30ml trichloromethane, 2g polycarbonate (in advance in 80 ℃ of following vacuum oven 24 hours) is dissolved in the 10ml trichloromethane, again with the two uniform mixing, is mixed with the solution that oxidant concentration is 40% (weight ratio).Step, reactions steps and the reaction conditions of all the other preparation films are together
Embodiment 1.
The thickness of polycarbonate membrane is about 0.34 millimeter.After reaction finished, polycarbonate membrane was by the original light yellow black that becomes, and specific conductivity is 1.71 * 10
-6S/cm.
Embodiment 4:
Earlier the 0.9g FERRIC CHLORIDE ANHYDROUS is dissolved in the 10ml tetrahydrofuran (THF), 1.8g APET (in advance in 80 ℃ of following vacuum oven 24 hours) is dissolved in the 20ml tetrahydrofuran (THF), again with the two uniform mixing, is mixed with the solution that oxidant concentration is 50% (weight ratio).The step of all the other preparation films obtains thickness and is 0.4 millimeter APET film with embodiment 1.
The film for preparing is put into autoclave simultaneously with new distillatory pyrrole monomer, and temperature is 33 ℃, and pressure is 8MPa, reacts 12 hours.After reaction finished, the APET film became black by original khaki color, and specific conductivity is 1.97 * 10
-3S/cm.
Embodiment 5:
Earlier the 0.9g FERRIC CHLORIDE ANHYDROUS is dissolved in the 10ml tetrahydrofuran (THF), 1.8g PVC (in advance in 80 ℃ of following vacuum oven 24 hours) is dissolved in the 20ml tetrahydrofuran (THF), again with the two uniform mixing, is mixed with the solution that oxidant concentration is 50% (weight ratio).The step of all the other preparation films obtains thickness and is 0.2 millimeter PVC film with embodiment 1.
The film for preparing is put into autoclave simultaneously with new distillatory pyrrole monomer, and temperature is 33 ℃, and pressure is 8MPa, reacts 12 hours.After reaction finished, the PVC film became black by original Vandyke brown, and specific conductivity is 1.24 * 10
-3S/cm.
Embodiment 6:
Earlier the 0.9g FERRIC CHLORIDE ANHYDROUS is dissolved in the 10ml tetrahydrofuran (THF), 1.8g EPDM is dissolved in 20ml tetrahydrofuran (THF)/toluene (50/50), again with the two uniform mixing, is mixed with the solution that oxidant concentration is 50% (weight ratio).The step of all the other preparation films obtains thickness and is 0.5 millimeter EPDM film with embodiment 1.
The film for preparing is put into autoclave simultaneously with new distillatory pyrrole monomer, and temperature is 33 ℃, and pressure is 8MPa, reacts 12 hours.After reaction finished, the EPDM film became black by original Vandyke brown, and specific conductivity is 6.22 * 10
-5S/cm.
Embodiment 7:
Earlier the 0.6g FERRIC CHLORIDE ANHYDROUS is dissolved in the 10ml tetrahydrofuran (THF), sulfonation degree is that the zinc salt 1.8g of 5.96% sulfonated polystyrene is dissolved in the 20ml tetrahydrofuran (THF).With the two uniform mixing, be mixed with the solution that oxidant concentration is 33.3% (weight ratio), solution is poured on sheet glass upper berth film, treat to transfer to 40 ℃ of vacuum oven 48 hours after solvent volatilizees to the greatest extent substantially, obtain the sulfonated polystyrene film that is mixed with the oxygenant iron trichloride that thickness is about 0.28 millimeter.
The film for preparing is put into autoclave simultaneously with new distillatory pyrrole monomer, and temperature is 40 ℃, and pressure is 8MPa, reacts 20 minutes.After reaction finished, Polystyrene Film became black by original khaki color, and specific conductivity is 1.42 * 10
-4S/cm.
Embodiment 8:
Earlier the 1.2g FERRIC CHLORIDE ANHYDROUS is dissolved in the 10ml tetrahydrofuran (THF), sulfonation degree is that the zinc salt 1.8g of 5.96% sulfonated polystyrene is dissolved in the 20ml tetrahydrofuran (THF).With the two uniform mixing, be mixed with the solution that oxidant concentration is 66.7% (weight ratio), solution is poured on sheet glass upper berth film, treat to transfer to 40 ℃ of vacuum oven 48 hours after solvent volatilizees to the greatest extent substantially, obtain the sulfonated polystyrene film that is mixed with the oxygenant iron trichloride that thickness is about 0.18 millimeter.
The film for preparing is put into autoclave simultaneously with new distillatory pyrrole monomer, and temperature is 40 ℃, and pressure is 20MPa, reacts 12 hours.After reaction finished, Polystyrene Film became black by original khaki color, and specific conductivity is 0.21S/cm.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021045267A CN1202163C (en) | 2002-02-08 | 2002-02-08 | Supercritical CO2 process of preparing conductive composite polypyrrole film material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021045267A CN1202163C (en) | 2002-02-08 | 2002-02-08 | Supercritical CO2 process of preparing conductive composite polypyrrole film material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1436807A CN1436807A (en) | 2003-08-20 |
| CN1202163C true CN1202163C (en) | 2005-05-18 |
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| US7048968B2 (en) * | 2003-08-22 | 2006-05-23 | Micron Technology, Inc. | Methods of depositing materials over substrates, and methods of forming layers over substrates |
| FI116626B (en) * | 2004-01-27 | 2006-01-13 | Valtion Teknillinen | Process for precipitating conductive polymer coatings in supercritical carbon dioxide |
| CN1313191C (en) * | 2004-09-24 | 2007-05-02 | 浙江大学 | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology |
| CN100444438C (en) * | 2007-03-01 | 2008-12-17 | 上海交通大学 | A method for improving the methanol permeation resistance of fluorine-containing sulfonic acid type proton exchange membrane |
| CN101818358B (en) * | 2009-12-28 | 2012-06-13 | 上海大学 | Supercritical CO2 high temperature and high pressure synthesis polymer conductive film device |
| CN105061731A (en) * | 2015-07-31 | 2015-11-18 | 天津大学 | Method for constructing multistage morphology polypyrrole membrane based on in situ wrinkling and thermal expansion |
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