CN1706870A - Monocrystalline organic micron/nanometer polymer particle and its fast polymerizing and crystallizing plasma process - Google Patents
Monocrystalline organic micron/nanometer polymer particle and its fast polymerizing and crystallizing plasma process Download PDFInfo
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Abstract
The present invention provides one kind of fast polymerizing and crystallizing plasma process suitable for forming monocrystalline micro/nanometer particle of various conjugate and non-cnjugate organic polymer. By means of dielectric blocking discharge at normal temperature and normal pressure, polymer is first cracked into active monomer particles and the active monomer particles are then orienting polymerized to form deposited film of monocrystalline micro/nanometer polymer particles on the surface of substrate within decades seconds. These micro/nanometer particles exhibit complete monocrystalline structures arranged orientedly on the surface of substrate with length/diameter ratio of 1-5000, nanometer level to millimeter level length, outer diameter of 20-1000 nm, wall thickness of 10-900 nm and polymer molecular weight of 1,000-1,000,000.
Description
Technical field
The present invention relates to plasma body confinement polymerization shaping field, specifically is about monocrystalline organic polymer micro-/ nano particle and plasma body rapid polymerization crystallization manufacturing process thereof.
Background technology
Accurate one-dimensional single crystal polymer nano material has a lot of ideal behaviores.Since on the macromolecular chain between atom each other covalency link to each other, and in the space regular ordered arrangement, its mechanical property will be near the constant intensity of chemical bond on the molecular backbone chain; Simultaneously, owing to impurity, crystal boundary, defective reduce, carrier mobility improves greatly, helps to obtain high-quality photoelectric functional polymkeric substance, and demonstrates and accurate one-dimensional inorganic, the different nano-meter characteristic of metal nano material.
But the acquisition of accurate one-dimensional single crystal polymer nano material is quite difficult.If adopt the method for " from top to bottom ", after polymer macromolecule is synthetic, will reach again and generate thousand up to ten thousand atoms on the micron-sized molecular chain along the regular arrangement of one dimension direction, the kinetics obstacle is very big, usually also can only obtain the folded chain platy-monocrystal polymkeric substance of thickness tens nanometers by extremely rare solution, extremely long time, although perhaps adopt the booster action of electrostatic force, mechanical stretching force, the nanofiber that can only obtain also that crystallinity is poor, mechanical property and conventional ultra-fine fibre is as good as is difficult to obtain single crystal structure; If adopt the template polymerization method of " from bottom to top ", utilize catalyzer and various soft, rigid template, as the micropore of various micella molecules, lipoid molecule, mesoporous material, liquid crystal molecule etc. and ordered structure etc. as the restriction mould, catalyzed polymerization in template restriction duct, remove template forming again, above-mentioned kinetics obstacle in the time of can avoiding the macromolecular chain crystallization just is self-assembled into the one dimension Nano structure polymkeric substance with organic molecule simultaneously at polymeric.Make template electrolytic polymerization thiophene in boron trifluoride ether solution as the high full group of stone by the microporous aluminum oxide filtering membrane and obtain the nanotube of 20-200nm, and have higher-strength (M.X.Fu, etal., Adv.Mater.13,1874 (2001)); Yao builds the self-induction rod-shaped micelle confinement template that year group provides by utilizing tensio-active agent methyl brometo de amonio, and 1,3-phenylbenzene-interactional the synergistic effect of the intermolecular π-π of 2-pyrazoline (DP), but the J-aggressiveness that obtain a kind of electroluminescent, shows the special optical performance is piled up the nanofiber (H.B.Fu form, et al., Angew.Chem..Int.Ed.42,2883 (2003)); Ten thousand Mei Xiang groups obtain to have photoactive partial crystallization polyaniline nano pipe (Y.S.Yang and M.X.Wan, J.Mater.Chem.12,897 (2002)) by pyrrolidone carboxylic acid's real-time doped polymeric; Akagi group is by Ziegler-Natta catalyst and the synthetic volution polyacetylene nanofiber (K.Akagi et al., Science 282:1683 (1998)) of the orderly template of liquid crystal; Martin group synthesized all kinds of polymer nanocomposite periosteums such as polypyrrole (S.D.Vito and C.R.Martin, Chem.Mater.10,1738 (1998)) by the template polymerization method.But because the regularity of template self is still waiting perfect at present, template also often need be further purified with catalyzer separates, thereby the purity, taxis and the spacial ordering that have influenced the self-assembly crystalline polymer are arranged, be difficult to obtain single crystal structure, the nano functional sex expression of product gets neither be very good, thereby this template also fails to solve the difficult problem that accurate one-dimensional single crystal polymer nano material crystallization is shaped.Synthetic single crystal polymer nano material, especially accurate one-dimensional single crystal polymer nanocomposite structure and explore its new manufacturing process with mechanism remain very necessary.
Summary of the invention
The purpose of this invention is to provide organic polymer monocrystalline micro-/ nano particle, especially accurate one-dimensional single crystal organic polymer micro-/ nano particle; Another object of the present invention provides monocrystalline organic polymer micro-/ nano particulate plasma body rapid polymerization crystallization manufacturing process.
Monocrystalline organic polymer micro-/ nano particle performance of the present invention goes out complete single crystal structure, can align at substrate material surface.The length-to-diameter ratio variation range is 5000: 1-1: 1, and length is an extremely millimeter magnitude of nanometer, external diameter is the 20-1000 nanometer, wall thickness 10-900 nanometer, polymericular weight 1000-1000000.
Monocrystalline organic polymer micro-/ nano shaping particles method of the present invention, be that monomer with the reactant gases organic polymer mixes with the carrier gas rare gas element, feed in the normal temperature and pressure dielectric barrier discharge plasma reactor, polyreaction 10 seconds～30 minutes, the reaction gaseous product can form a large amount of monocrystalline polymer micron/nano particles by the substrate material surface in inserting reactor, the body material temperature is controlled at 1 ℃～100 ℃, perhaps will react gaseous product and directly introduce in the solution such as ethanol, water, acetone, can obtain monocrystalline polymer micron/nano particle suspension liquid.
Concrete steps are as follows:
Adopt dielectric barrier discharge plasma reactor as shown in Figure 1.At normal temperatures and pressures, adopt commercially available high-voltage ac power, apply High Level AC Voltage on the electrode, adjustable frequency 10Hz～100kHz, and use pulsed modulation, the pulse time of " opening " can be 1 μ s～90ms, it is 1%～100% that the time of " opening " accounts for the total pulse widths time (pulse duty factor), voltage 5000～30000V, high voltage electrode are latten(-tin) or stainless steel substrates, reach electrode width 0.1～20mm between the control high voltage electrode.Insert a medium layer between reactor inner high voltage electrode and ground-electrode, medium layer can be glass, mica, quartz, tetrafluoroethylene, aluminium sesquioxide etc., thickness 1mm～15mm.Discharge power 200～2000W.
Polymer monomer is various gaseous states or the liquid non-structure organic molecule of gripping altogether or grip altogether,, benzylidene chloride grand as methane, ethane, propane, butane, ethene, propylene, divinyl, isoprene, vinylbenzene, acetylene, vinylformic acid, methyl methacrylate, phenyl-hexafluoride, tetrafluoromethane, HFC-236fa, tetrafluoroethylene, zellon, acrylonitrile, pyrroles, thiophene, aniline, ethene quinoline, vinyl carbazole, quinoxaline, pyrrole or the like.Rare gas element such as nitrogen, helium, neon, argon etc.Rare gas element and monomeric ratio of mixture are 0～800: 1.Adopt gas mixer with rare gas element and reactant gases thorough mixing, be made into the mixed gas of aforementioned proportion, by mass flow controller control mixed gas flow, making reactor pressure is 600～1000mmHg.
The body material ultrasonic cleaning is clean, place plasma reactor, these body materials can be glass, silicon chip, quartz, aluminium sesquioxide, polyester film sheet, cotton, fiber crops, silk synthon, fabric etc.Body material ionization electrode distance 0.1～30mm.Feed rare gas element 5min, close the back and feed a certain proportion of reaction mixture gas body that configures, apply High Level AC Voltage on the electrode after, produce plasma discharge in the reactor, discharge polymerisation 10s～30min deposits in substrate material surface monomer generation polymerization.Discharge finishes, and powered-down and source of the gas take out body material, obtains to include a large amount of monocrystalline polymer micron/nano particulate deposited films on its surface.Or gaseous product introduced in each kind solvent such as water or ethanol, promptly obtain to contain monocrystalline polymer micron/nano particulate suspension.
The micro-/ nano particle that obtains is organic polymer by infrared (FTIR), x-ray photoelectron power spectrum (XPS) and gel permeation chromatography (GPC) test as can be known, and molecular weight can reach 1000～1000000; Scanning electronic microscope (SEM) detects as can be known, is the micro-/ nano particle of various geometric shapes such as various tubuloses, bar-shaped, spherical shape, square, sexangle; X-ray diffraction (XRD) and transmission electron microscope detect (TEM) as can be known, the micro-/ nano particle be six sides, cube, all kinds of single crystal structure such as monocline.
Grip altogether the monocrystalline polymer micron/nano of structure particle doped after, can be used as various accurate one dimension micro-/ nano molecular wires; Micro-/ nano electrode, electromagnetic shielding material, battery, photic, electrochromic display device, transmitter etc.; Non-grip altogether or non-adulterated monocrystalline polymer micron/nano particle can be used as all kinds of micro-/ nano insulating sheaths is used for micro-/ nano cable, optical cable, pharmaceutical carrier, embedding medium etc.; Also can be used for polymkeric substance and only need one dimension reinforced composite field etc.
The present invention has following advantage:
1, the micro-/ nano particle has the monocrystalline polymer architecture.The theoretical investigation that it both can be polymkeric substance provides the theoretical model material, crystal boundary, defective, impurity of crystalline polymer etc. have been overcome again greatly, it is big to grip length altogether, the carrier mobility height, all kinds of molecular wires, optical element, the circuit that can be used for high mechanical strength, or provide accurate one-dimensional single crystal strongthener for matrix material.
2, polymerization process is fast and convenient, carries out near normal temperature and pressure, just can obtain to contain the polymkeric substance crystal grain of a large amount of monocrystalline micro within tens of seconds; Do not need additional template, catalyzer etc., saved numerous and diverse tediously long crystallisation process, and the removal process of additional template catalyzer; Acquisition product purity height does not contain other impurity.
3, monocrystalline polymer micron/nano particulate geometric shape and chemical structure can be controlled by the adjusting of reaction conditions, both can be particles such as 1: 1 circle of length-to-diameter ratio, square, sexangle, also can be 5000: 1 one dimension micro-/ nano pipeline of length-to-diameter ratio; And can form the array of partially oriented arrangement; Or certain density suspension.
4, adapt to the coating or the assembling of all kinds of baseplate material surface aggregate thing monocrystalline micro-/ nano membrana granulosas, can batch production or continuous production.
Description of drawings
Fig. 1 is the synoptic diagram of dielectric barrier discharge plasma reactor.
1-reactant gases 2-carrier gas among the figure
3-gas mixer 4-under meter
5-plasma reactor 6-carrier gas outlet
7-high voltage electrode 8-medium layer
9-body material 10-ground-electrode
Fig. 2 is the electron scanning micrograph of the poly-fluorine carbon monocrystalline micron tube of one embodiment of the invention formation.Nanotube outside diameter 800nm, thickness of pipe 130nm, hexagonal section.
Fig. 3 is the Fourier infrared spectrum of the poly-fluorine carbon-nano pipe of another embodiment of the present invention formation, 480cm
-1Be the asymmetric and symmetrical rocking vibration of CF peak.735cm
-1Be CF formation vibration peak.Be shown as FC organic polymer structure.
Poly-fluorocarbon polymer nano wire and TEM single crystal diffraction spot thereof that Fig. 4 forms for further embodiment of this invention, external diameter 300nm is shown as face-centered cubic crystalline texture, and unit cell parameters a is 5.786 .
Fig. 5 reaches 0.5mm, diameter 300nm for the polypyrrole monocrystal nanowire SEM figure that another embodiment of the present invention forms.
The polypyrrole monocrystal nanowire TEM diffraction single-crystal lattice structure iron that Fig. 6 forms for another embodiment of the present invention, interplanar distance 2.5 .
The polypyrrole nanometer monocrystalline particulate electron scanning micrograph that Fig. 7 forms for another embodiment of the present invention, about long 2000 nanometers, approximate fusiform.
The polypyrrole nanometer monocrystalline particulate electron scanning micrograph that Fig. 8 forms for another embodiment of the present invention, approximate sexangle.
Fig. 9 is a continuum barrier discharge plasma reactor synoptic diagram
Embodiment
Embodiment 1, adopts plasma reactor shown in Figure 1, supply frequency 50Hz, and power 0.2Kw, pulse duty factor 10%, block media is AL
2O
3, stainless steel electrode, high voltage electrode width 0.1mm, the wide 20mm of interpolar.
The simple glass ultrasonic cleaning is clean, place apart from high voltage electrode 0.1mm place, feed straight argon and CF
4Mixed gas, ratio of mixture 2: 1, total flux 0.3SLM, pressure 760mmHg, discharge is taken out sample behind the 10S.SEM is viewed as the poly-fluorocarbon polymer micron tube of partially oriented arrangement as shown in Figure 2.External diameter of pipe 800nm, internal diameter 540nm, long 30nm, the cross section is similar to regular hexagon, and FTIR and XPS are shown as F, C, O composition, and the F/C/O ratio is 1: 3: 0.02, and XRD and TEM result are shown as monocrystalline simple cubic structure, and the GPC determining molecular weight is 100000.
Embodiment 2, adopt plasma reactor shown in Figure 1, supply frequency 98000Hz, and power 1.8Kw, pulse duty factor 100%, block media is a mica, stainless steel electrode, high voltage electrode width 18mm, the wide 2mm of interpolar.
The quartz plate ultrasonic cleaning is clean, place apart from high voltage electrode 4.0mm place, feed pure helium and C
6F
6Mixed gas, ratio of mixture 7: 1, pressure 900mmHg, discharge is taken out sample behind the 1500S.SEM is viewed as the poly-fluorine carbon-nano pipe of partially oriented arrangement.External diameter of pipe 500nm, internal diameter 300nm, the cross section is similar to regular hexagon, length-to-diameter ratio 60: 1, XRD and TEM result are shown as the monocrystalline hexagonal structure, and unit cell parameters a is 6.562 , and c is 9.451 , and the GPC determining molecular weight is 950000.As Fig. 3 is this fluorocarbon polymer infrared spectra.
Embodiment 3, adopt plasma reactor shown in Figure 1, supply frequency 5000Hz, and power 1.5Kw, pulse duty factor 80%, block media is quartzy, copper electrode, high voltage electrode width 15mm, the wide 15mm of interpolar.
The silicon chip ultrasonic cleaning is clean, place apart from high voltage electrode 3.0mm place, feed straight argon and C
3F
6Mixed gas, ratio of mixture 100: 1, pressure 800mmHg, discharge 600S takes out sample.SEM is viewed as the poly-fluorocarbon polymer micro-nano mitron of partially oriented arrangement, external diameter of pipe 300nm, cross section approximate circle shape, FTIR and XPS are shown as F, C, O composition, the F/C/O ratio is 1: 1.9: 0.2, length-to-diameter ratio 30: 1, XRD and TEM result are shown as the monocrystalline face-centred cubic structure, and the GPC determining molecular weight is 100000.For gathering fluorocarbon polymer nano wire and TEM single crystal diffraction spot thereof, be shown as face-centered cubic crystalline texture as Fig. 4;
Embodiment 4, adopt plasma reactor shown in Figure 1, supply frequency 100Hz, and power 0.2Kw, pulse duty factor 85%, block media is AL
2O
3, stainless steel electrode, high voltage electrode width 0.2mm, the wide 10mm of interpolar.
The simple glass ultrasonic cleaning is clean, place apart from high voltage electrode 0.1mm place, feed the mixed gas of straight argon and butane, ratio of mixture 100: 1, total flux 0.3SLM, pressure 760mmHg takes out sample behind the discharge 30S.SEM is viewed as the poly-butane micron tube of partially oriented arrangement.FTIR and XPS are shown as H, C, O composition, and the H/C/O ratio is 0.3: 7: 0.02, and XRD and TEM result are shown as the monocrystalline body-centered cubic structure, and the GPC determining molecular weight is 90000.
Embodiment 5, adopt plasma reactor shown in Figure 1, supply frequency 80Hz, and power 1.5Kw, pulse duty factor 90%, block media is quartzy, copper electrode, high voltage electrode width 0.1mm, the wide 15mm of interpolar.
The silicon chip ultrasonic cleaning is clean, place apart from high voltage electrode 3.0mm place, feed purity nitrogen and cinnamic mixed gas, ratio of mixture 200: 1, pressure 780mmHg, discharge 300S takes out sample.SEM is viewed as the polystyrene micro-nano mitron of partially oriented arrangement, FTIR and XPS are shown as H, C, O composition, and the H/C/O ratio is 0.5: 7.3: 0.2, length-to-diameter ratio 30: 1, XRD and TEM result are shown as the monocrystalline face-centred cubic structure, and the GPC determining molecular weight is 100000.
Embodiment 6, adopt plasma reactor shown in Figure 1, supply frequency 300Hz.Power 1.0Kw, pulse duty factor 75%, block media is a tetrafluoroethylene, copper electrode, high voltage electrode width 0.5mm, the wide 10mm of interpolar.
The sheet glass ultrasonic cleaning is clean, place apart from high voltage electrode 5.0mm place, feed straight argon and acrylic acid mixed gas, ratio of mixture 100: 1, pressure 760mmHg takes out sample behind the discharge 180S.SEM is viewed as the polyacrylic acid nano line.FTIR and XPS are shown as C, H, O composition, and the C/H/O ratio is 5: 2.3: 0.7.Length-to-diameter ratio 5000: 1, XRD and TEM result are shown as the cubic monocrystalline structure, and the GPC determining molecular weight is 300000.
Embodiment 7, adopt plasma reactor shown in Figure 1, supply frequency 30000Hz.Power 1.0Kw, pulse duty factor 50%, block media is quartzy, stainless steel electrode, high voltage electrode width 10mm, the wide 10mm of interpolar.
The sheet glass ultrasonic cleaning is clean, place apart from high voltage electrode 2.0mm place, feed straight argon and pyrroles's mixed gas, ratio of mixture 500: 1, pressure 760mmHg takes out sample behind the discharge 480S.SEM is viewed as the polypyrrole polymers nano wire.As shown in Figure 5, line external diameter 300nm, cross section approximate circle shape; FTIR and XPS are shown as C, N, H, O composition, and the C/N/H/O ratio is 4: 1: 2.6: 0.2, and length-to-diameter ratio 5000: 1, XRD and TEM result are shown as the monocrystalline monocline, and the GPC determining molecular weight is 800000.
Embodiment 8, adopt plasma reactor shown in Figure 1, supply frequency 1500Hz, and power 0.8Kw, pulse duty factor 100%, block media is a tetrafluoroethylene, copper electrode, high voltage electrode width 8mm, the wide 3mm of interpolar.
The sheet glass ultrasonic cleaning is clean, place apart from high voltage electrode 1.0mm place, feed straight argon and pyrroles's mixed gas, ratio of mixture 300: 1 is 600mmHg by vacuum system pressure, takes out sample behind the discharge 180S.SEM is viewed as the polypyrrole polymers nano wire.Line external diameter 80nm, the cross section is similar to sexangle (as shown in Figure 8), FTIR and XPS are shown as C, N, H, O composition, the C/N/H/O ratio is 4.1: 1: 2.5: 0.3, length-to-diameter ratio 3000: 1, XRD and TEM result are shown as face-centred cubic structure, TEM diffraction lattice structure as shown in Figure 6, the GPC determining molecular weight is 500000.
With the ultrasonic wash clean of simple glass, place apart from high-pressure stage 4mm place, feed pure argon and pyrroles's mixed gas, ratio of mixture 300: 1, pressure 760mmHg takes out sample behind the discharge 4min.SEM is viewed as the fusiform nano-crystalline granule of polypyrrole polymers as shown in Figure 7, length-to-diameter ratio 10: 1, FTIR and XPS are shown as C, N, H, O composition, and the C/N/H/O ratio is 4: 1: 2.5: 0.1, XRD and TEM result are shown as the simple cubic structure, and the GPC determining molecular weight is 600000.
With the ultrasonic wash clean of simple glass, place apart from high-pressure stage 3mm place, feed the mixed gas of pure nitrogen gas and aniline, ratio of mixture 300: 1, pressure 760mmHg takes out sample behind the discharge 120s.FTIR and XPS are shown as C, N, H, O composition, and the C/N/H/O ratio is 5: 1: 2.7: 0.2, and XRD and TEM result are shown as the monocrystalline face-centred cubic structure, and the GPC determining molecular weight is 900000.
Embodiment 11, adopt plasma reactor shown in Figure 1, supply frequency 1300Hz, and power 0.6Kw, pulse duty factor 80%, block media is quartzy, copper electrode, high voltage electrode width 0.2mm, the wide 0.9mm of interpolar.
With the ultrasonic wash clean of simple glass, place apart from high voltage electrode 4mm place, feed the mixed gas of pure argon and thiophene, ratio of mixture 500: 1, pressure 760mmHg takes out sample behind the discharge 100s.FTIR and XPS are shown as C, S, H, O composition, and the C/S/H/O ratio is 4.2: 1: 1: 0.5, and XRD and TEM result are shown as the monocrystalline monocline, and the GPC determining molecular weight is 700000.
Embodiment 12, adopt plasma reactor shown in Figure 1, supply frequency 1200Hz, and power 1.0Kw, pulse duty factor 85%, block media is a tetrafluoroethylene, stainless steel electrode, high voltage electrode width 0.1mm, the wide 0.8mm of interpolar.
With the ultrasonic wash clean of simple glass, place apart from high voltage electrode 4mm place, feed the mixed gas of pure argon and benzylidene chloride, ratio of mixture 400: 1, pressure 760mmHg takes out sample behind the discharge 180s.FTIR and XPS are shown as C, Cl, H, O composition, and the C/Cl/H/O ratio is 6.2: 1.2: 2.0: 8, and XRD and TEM result are shown as the simple cubic structure, and the GPC determining molecular weight is 900000.
Embodiment 13, adopt plasma reactor shown in Figure 9, supply frequency 1200Hz, and power 1.5Kw, pulse duty factor 85%, block media is a tetrafluoroethylene, stainless steel electrode, high voltage electrode width 0.2mm, the wide 0.8mm of interpolar.
Place the electrode discharge reaction zone of continuum (tetrafluoroethylene) barrier discharge reactor to pass through argon gas and monomer C continuously the ultrasonic wash clean of fabric
3F
6Ratio of mixture is 500: 1, and pressure 780mmHg carries out plasma polymerization continuous discharge and handles under atmospheric pressure at room, and the take off roll rotating speed is 4 rev/mins, thereby can realize serialization production.The SEM observation sample is the poly-fluorocarbon polymer micro-/ nano pipe of partially oriented arrangement, and FTIR and XPS are shown as F, C, O composition, and the F/C/O ratio is 1: 1.7: 0.3, and XRD and TEM result are shown as the monocrystalline face-centred cubic structure, and the GPC determining molecular weight is 95000.
Claims (10)
1, a kind of monocrystalline organic polymer micro-/ nano particulate plasma body rapid polymerization crystallization manufacturing process, it is characterized in that the monomer of reactant gases organic polymer is mixed with the carrier gas rare gas element, feed in the normal temperature and pressure dielectric barrier discharge plasma reactor, polyreaction 10 seconds～30 minutes, gaseous product forms a large amount of monocrystalline micro polymers/sodium rice particle at the substrate material surface of inserting reactor, the body material temperature is controlled at 1-100 ℃, body material is 0.1-30mm from the high voltage electrode distance, rare gas element is 0-800 with the mixed volume ratio of reactant gases: 1, and it is 600～1000mmHg that both mixed gas flows make reactor pressure.
2, manufacturing process as claimed in claim 1 is characterized in that described polyreaction gaseous product can directly be introduced in etoh solvent, water or the acetone to obtain monocrystalline polymer micron/nano particle suspension liquid.
3, manufacturing process as claimed in claim 1 or 2, the monomer that it is characterized in that described reactant gases organic polymer are to be various gaseous states or liquid non-conjugated or conjugated structure organic molecule.
4, manufacturing process as claimed in claim 3, the monomer that it is characterized in that described reactant gases organic polymer is to be methane, ethane, propane, butane, ethene, propylene, divinyl, isoprene, vinylbenzene, acetylene, vinylformic acid, methyl methacrylate, zellon, tetrafluoroethylene, phenyl-hexafluoride, tetrafluoromethane, HFC-236fa, vinyl cyanide, pyrroles, thiophene, aniline, ethene quinoline, vinyl carbazole, quinoxaline, grand, the benzylidene chloride of pyrrole.
5, manufacturing process as claimed in claim 1 or 2 is characterized in that described rare gas element is nitrogen, helium, neon or argon gas.
6, manufacturing process as claimed in claim 1 or 2, the adjustable frequency that it is characterized in that described plasma reactor is 10Hz～100KHz, use pulsed modulation, the pulse time of " opening " is 1 μ s～90ms, it is 1%～100% that the time of " opening " accounts for the total pulse widths time, voltage 5000～30000V, reaching electrode width between high voltage electrode is 0.1～20mm.It is the medium layer of 1-15mm that one thickness is arranged between reactor inner high voltage electrode and ground-electrode, discharge power 200～2000W.
7, manufacturing process as claimed in claim 6 is characterized in that described medium layer is glass, mica, quartz, tetrafluoroethylene or aluminium sesquioxide.
8, manufacturing process as claimed in claim 6 is characterized in that described high voltage electrode is latten(-tin) or stainless steel substrates.
9, manufacturing process as claimed in claim 1 or 2 is characterized in that described body material is selected from glass, silicon chip, quartz, aluminium sesquioxide, polyester film sheet, cotton, fiber crops, silk synthon or fabric.
10, the prepared product monocrystalline organic polymer micro-/ nano particle of manufacturing process as claimed in claim 1 or 2, it is characterized in that the particle length-to-diameter ratio is 5000: 1-1: 1, length is that nanometer is to the millimeter magnitude, external diameter is the 20-1000 nanometer, wall thickness 10-900 nanometer, polymericular weight 1000-1000000.
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| CN110655641A (en) * | 2019-08-28 | 2020-01-07 | 北京印刷学院 | Method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ solid state polymerization |
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| CN110655641A (en) * | 2019-08-28 | 2020-01-07 | 北京印刷学院 | Method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ solid state polymerization |
| CN110655641B (en) * | 2019-08-28 | 2022-05-13 | 北京印刷学院 | Method for preparing conductive polythiophene and conductive paper by atmospheric pressure plasma in-situ solid state polymerization |
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