CN101619115B - High-temperature proton-exchange polymer film and preparation method thereof - Google Patents
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Abstract
The invention discloses a high-temperature proton-exchange polymer film and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing 20-50 monomer, 15-60 ionic liquid and 15-40 surfactant by weight percent for preparing microemulsion; and preparing proton-exchange polymer film by microemulsion polymerization. The monomer is selected from one or two components of styrene, sulfonated styrene, alpha-vinyltoluene, acrylonitrile, vinyl alcohol, alpha-methacrylonitrile, alpha, beta, beta-trifluorostyrene, alpha-methyl sulfonated styrene, methyl methacrylate, vinyl pyrrolidone or octafluoro styrene; and the ionic liquid is hydrophobic dendritic macromolecular ionic liquid. In the invention, the dendritic macromolecular ionic liquid is dispersed and fixed in the polymer film on a nano scale, and the doped dendritic macromolecular ionic liquid is not easy to wash out by water generated by a battery, thus, the stability of the proton-exchange polymer film in use is enhanced.
Description
Technical field
The present invention relates to a kind of fuel cell component and preparation method thereof, be specifically related to a kind of proton-exchange polymer film that can at high temperature use and preparation method thereof.
Background technology
That ionic liquid has is non-volatile, do not burn, almost do not have vapour pressure, is heated and can expand, and characteristics such as good conductivity are widely used in fields such as electrochemistry, organic synthesis, catalysis and extracting and separating.In recent years, ionic liquid also more and more comes into one's own in field of polymer technology.The article report is arranged, hydrophobic ionic liquids such as hydrophilic ionic-liquid such as Methylimidazole Tetrafluoroboric acid, Methylimidazole trifluoromethanesulfonic acid and Methylimidazole phosphofluoric acid, the two fluoroform sulfimides of Methylimidazole are doped in the polymeric membrane, obtain the higher polyelectrolyte film of specific conductivity (referring to: ChemPhysChem 2007,8,1103-1107; Macromolecules 2008,41,3389-3392; Chem.Mater.2009,21,1480-1484).
Publication number is to disclose in the Chinese invention patent application open file of CN101070397A a kind of ionic liquid to be doped to method in the polymeric film, obtains a kind of proton-exchange polymer film then.
Film all has a shortcoming described in the above-mentioned prior art scheme, and adulterated ionic liquid is all gone out by the washing that generates in the fuel cell use easily, thereby influences the use properties and the life-span of film.
Summary of the invention
The object of the invention provides a kind of high-temperature proton-exchange polymer film and preparation method thereof.
For achieving the above object, the concrete technical scheme of the present invention is that a kind of preparation method of high-temperature proton-exchange polymer film specifically may further comprise the steps:
With monomer, ionic liquid, tensio-active agent by weight 20～50: 15～60: 15～40 mix, and are mixed with microemulsion, carry out the micro-emulsion polymerization preparation and obtain proton-exchange polymer film.
In the technique scheme, adopt the ultrasonic wave effect when mixing microemulsion, be translucent or transparence until microemulsion.
In the technique scheme, described monomer is selected from: vinylbenzene, sulfonated phenylethylene, alpha-methyl styrene, vinyl cyanide, vinyl alcohol, Alpha-Methyl vinyl cyanide, α, β, one or both in β-trifluorostyrene, Alpha-Methyl sulfonated phenylethylene, methyl methacrylate, vinyl pyrrolidone or the octafluorostyrene;
Described ionic liquid is a hydrophobicity dendritic macromole ionic liquid, is selected from: the two fluoroform sulfimide ionic liquid PAMAM G2.0-NH of two generation polyamide-amides
3 +Tf
2N
-, the two fluoroform sulfimide ionic liquid PAMAM G3.0-NH of three generations's polyamide-amide
3 +Tf
2N
-Or the two fluoroform sulfimide ionic liquid PAMAM G4.0-NH of four generation polyamide-amides
3 +Tf
2N
-, two generation polyamide-amide phosphofluoric acid ionic liquid PAMAMG2.0-NH
3 +PF
6 -, three generations's polyamide-amide phosphofluoric acid ionic liquid PAMAM G3.0-NH
3 +PF
6 -Or four generation polyamide-amide phosphofluoric acid ionic liquid PAMAM G4.0-NH
3 +PF
6 -In a kind of; Described hydrophobicity dendritic macromole preparation method of ionic liquid comprises following concrete steps:
(1) with dendritic macromole polyamide-amine (PAMAM-NH
2, G2.0～G4.0) soluble in water slowly drips the nitric acid of equimolar amount, obtains polyamide-amide nitric acid (PAMAM-NH
3 +NO
3 -, G2.0～G4.0);
(2) add the two fluoroform sulfimide lithiums or the Potassium Hexafluorophosphate of equimolar amount then, after reaction is finished, the muddy liquid of oyster white becomes stratified two-phase, separatory is removed water layer, use distilled water wash again, rotary evaporation is removed methylene dichloride then, gets described hydrophobicity dendritic macromole ionic liquid after the vacuum-drying.
In the technique scheme, dendritic macromole polyamide-amine (PAMAM-NH
2, the preparation method of G2.0～G4.0) is referring to Zhou Yulan, Yang Yongli, Yang Hua etc. and the study on the synthesis of polyamide-amide dendritic macromole compound. Capital University of Medical Sciences's journal, 2001,22 (4): 321-326.
Described tensio-active agent is the polymerizable type ionic liquid emulsifier that contains ammonium ion, fragrant heterocycle structure, and the general formula that wherein contains the polymerizable type ionic liquid emulsifier of ammonium ion is:
The general formula that contains the polymerizable type ionic liquid emulsifier of ammonium ion is:
In the technique scheme, described polyreaction adopts microemulsion polymerization method; Described microemulsion polymerization method adopts thermal initiation, UV-light to cause or γShe Xianyinfajuhe.
The high-temperature proton-exchange polymer film that the present invention's claimed method for preparing of while obtains.
Simultaneously, be the comparative example to contain the ion liquid polymeric film of hydrophilic resin dendritic macromolecules, see embodiment one to four; Wherein, dendritic macromole polyamide-amine trifluoromethanesulfonic acid ionic liquid (PAMAM-NH
3 +TfO
-) ion liquid synthetic may further comprise the steps: with dendritic macromole polyamide-amine (PAMAM-NH
2, G2.0～G4.0) be dissolved in the methylene dichloride, ice-water bath slowly drips the trifluoromethanesulfonic acid of equimolar amount, reaction washes with water after finishing, separatory on a small quantity repeatedly, is removed water layer, rotary evaporation is removed methylene dichloride then, after the last room temperature vacuum-drying product.
Dendritic macromole polyamide-amine phosphate ion liquid (PAMAM G4.0-NH
3 +H
2PO
4 -, G2.0～G4.0) ion liquid synthesizing may further comprise the steps: with dendritic macromole polyamide-amine (PAMAMG4.0-NH
2, G2.0～G4.0) be dissolved in the methylene dichloride slowly drips the phosphoric acid of equimolar amount, reacts 48h, and reaction washes with water after finishing, and separatory is removed water layer, and rotary evaporation is removed methylene dichloride then, gets product after the last room temperature vacuum-drying.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1, the present invention creatively carries out micro-emulsion polymerization with the dendrimer ionic liquid with the film forming monomer, thus, the dendrimer ionic liquid is disperseed, is fixed in the polymeric film with the nanometer network structure, obtained a kind of new proton exchange membrane, adulterated dendrimer ionic liquid is difficult for being washed out, and has improved the stability of proton exchange membrane.
Description of drawings
Dendritic macromole and ion liquid TGA figure among Fig. 1: the embodiment 15;
Emulsifying agent HNMR figure among Fig. 2: the embodiment one;
The setting drawing of simulation electrolyzer among Fig. 3: the embodiment 16;
The composite membrane specific conductivity of Fig. 4: embodiment 16 doping different ionic liquid is with variation of temperature figure;
The stripping quantity and the time relation of the composite membrane of Fig. 5: embodiment 17 doping different ionic liquid;
Wherein, 1, Teflon material; 2, screw; 3, middle part sky; 4, the sample of film; 5, platinum electrode; 6, platinum filament.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +TfO
-) 0.15g, vinylbenzene 0.25g, vinyl cyanide 0.25g, tensio-active agent (b-Br) 0.35g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAMG4.0-NH transparent, that have certain physical strength after shining 40min down
3 +TfO
-Ionic liquid/St-co-AN polymer dielectric film.
Wherein, the preparation method of tensio-active agent b-Br can reference Feng Yan.Chem.Commun., and 2006,2696-2698.
The HNMR of tensio-active agent characterizes
Tensio-active agent adopts INOVA400MHZ nuclear magnetic resonance spectrum view, and TMS is interior mark, the results are shown in Figure 2.
Embodiment two:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +TfO
-) 0.30g, vinylbenzene 0.19g, vinyl cyanide 0.19g, tensio-active agent (b-Br) 0.32g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAMG4.0-NH transparent, that have certain physical strength after shining 40min down
3 +TfO
-Ionic liquid/St-co-AN polymer dielectric film.
Embodiment three:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +H
2PO
4 -) 0.15g, vinylbenzene 0.25g, vinyl cyanide 0.25g, tensio-active agent (b-Br) 0.35g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAMG4.0-NH transparent, that have certain physical strength after shining 40min down
3 +H
2PO
4 -Ionic liquid/St-co-AN polymer dielectric film.Released ion liquid is 30% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment four:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +H
2PO
4 -) 0.30g, vinylbenzene 0.19g, vinyl cyanide 0.19g, tensio-active agent (b-Br) 0.32g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAMG4.0-NH transparent, that have certain physical strength after shining 40min down
3 +H
2PO
4 -Ionic liquid/St-co-AN polymer dielectric film.Released ion liquid is 32% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment five:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +Tf
2N
-) 0.15g, vinylbenzene 0.25g, vinyl cyanide 0.25g, tensio-active agent (1-2-(acryloyl-oxy undecyl)-3-methyl imidazolium tetrafluoroborate) 0.35g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAM G4.0-NH transparent, that have certain physical strength after shining 40min down
3 +Tf
2N
-Ionic liquid/St-co-AN polymer dielectric film.Released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment six:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +Tf
2N
-) 0.30g, vinylbenzene 0.19g, vinyl cyanide 0.19g, tensio-active agent (1-2-(acryloyl-oxy undecyl)-3-methyl imidazolium tetrafluoroborate) 0.32g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAM G4.0-NH transparent, that have certain physical strength after shining 40min down
3 +Tf
2N
-Ionic liquid/St-co-AN polymer dielectric film.Released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment seven
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +Tf
2N
-) 0.15g, alpha-methyl styrene 0.25g, vinyl alcohol 0.25g, tensio-active agent (1-(2-acryloyl-oxy undecyl)-3-Methylimidazole Bromide) 0.35g, Diisopropyl azodicarboxylate 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, be heated to 70 ℃, 12h obtains PAMAM G4.0-NH transparent, that have certain physical strength
3 +Tf
2N
-Ionic liquid/St-co-AN polymer dielectric film.Released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment eight:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +Tf
2N
-) 0.30g, sulfonated phenylethylene 0.19g, vinyl cyanide 0.19g, tensio-active agent (1-(2-methacryloxypropyl undecyl)-3-methyl imidazolium tetrafluoroborate) 0.32g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, behind the γShe Xianyinfajuhe 40min, obtain PAMAM G4.0-NH transparent, that have certain physical strength
3 +Tf
2N
-Ionic liquid/St-co-AN polymer dielectric film.Released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment nine:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +PF
6 -) 0.15g, α, β, β-trifluorostyrene 0.25g, Alpha-Methyl vinyl cyanide 0.25g, tensio-active agent (the two fluoroform sulphonates of 1-(2-acryloyl-oxy undecyl)-3-Methylimidazole) 0.35g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAM G4.0-NH transparent, that have certain physical strength after shining 40min down
3 +PF
6 -Ionic liquid/St-co-AN polymer dielectric film.Released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment ten:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +PF
6 -) 0.30g, vinylbenzene 0.19g, vinyl cyanide 0.19g, tensio-active agent (1-(2-methacryloxypropyl undecyl)-3-Methylimidazole hexafluorophosphate) 0.32g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAM G4.0-NH transparent, that have certain physical strength after shining 40min down
3 +PF
6 -Ionic liquid/St-co-AN polymer dielectric film.Released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment 11:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +PF
6 -) 0.15g, methyl methacrylate 0.25g, vinyl cyanide 0.25, tensio-active agent (1-(2-acryloyl-oxy undecane oxygen base) trimethylammonium bromide salt) 0.35g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAM G4.0-NH transparent, that have certain physical strength after shining 40min down
3 +PF
6 -Ionic liquid/St-co-AN polymer dielectric film, released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment 12:
In reaction vessel, add four generation dendritic macromole ionic liquid (PAMAMG4.0-NH successively
3 +Tf
2N
-) 0.30g, vinyl pyrrolidone 0.19g, vinyl cyanide 0.19, tensio-active agent (1-(2-acryloyl-oxy undecane oxygen base) trimethylammonium phosphofluoric acid ammonium salt) 0.32g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAM G4.0-NH transparent, that have certain physical strength after shining 40min down
3 +Tf
2N
-Ionic liquid/St-co-AN polymer dielectric film, released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment 13:
In reaction vessel, add The Trees of Three Generations dendritic macromolecules ionic liquid (PAMAMG3.0-NH successively
3 +PF
6 -) 0.30g, octafluorostyrene 0.19g, vinyl cyanide 0.19, tensio-active agent (1-(2-acryloyl-oxy undecane oxygen base) trimethylammonium trifluoromethanesulfacid acid ammonium salt) 0.32g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAM G3.0-NH transparent, that have certain physical strength after shining 40min down
3 +PF
6 -Ionic liquid/St-co-AN polymer dielectric film, released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment 14:
In reaction vessel, add two generation dendritic macromole ionic liquid (PAMAMG2.0-NH successively
3 +Tf
2N
-) 0.30g, Alpha-Methyl sulfonated phenylethylene 0.19g, vinyl cyanide 0.19, tensio-active agent (b-Br) 0.32g, light trigger (Benzoin ethyl ether) 0.015g, linking agent (Vinylstyrene) 0.002g, under action of ultrasonic waves, present transparent or semitransparent state, mixing liquid is poured between two sheet glass then, the placement ultraviolet lamp obtains PAMAMG2.0-NH transparent, that have certain physical strength after shining 40min down
3 +Tf
2N
-Ionic liquid/St-co-AN polymer dielectric film, released ion liquid is 10% of film gross weight behind the soaked 40mins of gained film, does not have stripping behind the soaked 2h substantially again.
Embodiment 15: ion liquid TGA test
Dendritic macromole and the ion liquid thermotolerance of preparation dendritic macromole are all used thermal analyzer SDTQ600 (U.S. TA company).
The results are shown in Figure 1, Fig. 1 is dendritic macromole PAMAM G4.0-NH
2With ionic liquid PAMAMG4.0-NH
3 +Tf
2N
-TGA figure, the result shows that dendritic macromole just begins to decompose in the time of 120 ℃, the ion liquid degradation temperature of dendritic macromole then is 210 ℃.
Embodiment 16: the test of specific conductivity
Be assembled into the simulation electrolyzer, device entirely is pressed in the ionic liquid/polymer film on two electrode surfaces as Fig. 3, and the electrode outside is the Teflon pressing plate, and Teflon plate up and down is tightly compacted to guarantee that film contacts with the perfection of electrode.Two electrodes are drawn lead, and (Zahner 1M6EX) links to each other with electrochemical workstation.Assembly can be put into resistant to elevated temperatures closed unit, heats.
Adopt the specific conductivity of AC impedence method test membrane, exchanging the perturbation amplitude in the test process is 10mV, and range of frequency is 10～1MHz.The body resistance value Rb of film gets Z '-Z " abscissa value that curve medium-high frequency semicircle is corresponding with the low frequency straight-line intersection, if when the not too high or system specific conductivity of test frequency is higher, the high frequency semicircle does not occur, Rb gets the abscissa value of high frequency end points.Calculate the specific conductivity of film under certain temperature according to following calculation formula:
σ＝d/Rb?S
Wherein: σ is proton conductivity (S/cm); D is the thickness (cm) of dielectric film; Rb is the body resistance of dielectric film; S is the contact area (cm of electrode and dielectric film
2).
The results are shown in Figure 4: along with the rising of temperature, the specific conductivity of film progressively increases, and under uniform temp, three kinds of ion liquid specific conductivity sizes of anionic dendritic macromole are followed successively by σ (PAMAM-NH
3 +HSO
4 -)＞σ (PAMAM-NH
3 +H
2PO
4 -)＞σ (PAMAM-NH
3 +Tf
2N
-), when temperature reaches 160 ℃, doping dendritic macromole PAMAM-NH
3 +H
2PO
4 -The specific conductivity of composite membrane can reach 2.2 * 10
-3S/cm.
Embodiment 17: the stripping property test of composite membrane
Composite membrane with three kinds of 30% different ionic liquid of mixing after 105 ℃ of constant weights, places 50ml distilled water with the 0.2g film, to certain hour, film is taken out, and oven dry is weighed, and calculates the ionic liquid seepage discharge, triplicate.
The results are shown in Figure 5, show: the composite membrane of doping small molecular ion liquid, behind 20mins, all washed out basically.The ion liquid composite membrane of doping macromole hydrophobic type, the ionic liquid in the composite membrane are difficult to be washed out, and behind the soaked 2h, the ionic liquid recoverable amount still reaches 90%.
Embodiment 18:
The atomic force microscope test result of composite membrane shows: macromole dendroid ionic liquid is dispersed in the macromolecular material by well-proportioned, forms to have the polymer film structure of stable proton transport passage.
Claims (3)
1. the preparation method of a high-temperature proton-exchange polymer film is characterized in that, specifically may further comprise the steps:
With monomer, ionic liquid, tensio-active agent by weight 20～50: 15～60: 15～40 mix, and add the divinyl benzene crosslinked agent, are mixed with microemulsion, carry out the micro-emulsion polymerization preparation and obtain proton-exchange polymer film;
Described monomer is selected from: vinylbenzene, sulfonated phenylethylene, alpha-methyl styrene, vinyl cyanide, vinyl alcohol, Alpha-Methyl vinyl cyanide, α, β, one or both in β-trifluorostyrene, Alpha-Methyl sulfonated phenylethylene, methyl methacrylate, vinyl pyrrolidone or the octafluorostyrene;
Described ionic liquid is a hydrophobicity dendritic macromole ionic liquid, is selected from: the two fluoroform sulfimide ionic liquid PAMAM G2.0-NH of two generation polyamide-amides
3 +Tf
2N
-, the two fluoroform sulfimide ionic liquid PAMAM G3.0-NH of three generations's polyamide-amide
3 +Tf
2N
-Or the two fluoroform sulfimide ionic liquid PAMAM G4.0-NH of four generation polyamide-amides
3 +Tf
2N
-, two generation polyamide-amide phosphofluoric acid ionic liquid PAMAM G2.0-NH
3 +PF
6 -, three generations's polyamide-amide phosphofluoric acid ionic liquid PAMAM G3.0-NH
3 +PF
6 -Or four generation polyamide-amide phosphofluoric acid ionic liquid PAMAM G4.0-NH
3 +PF
6 -In a kind of;
The general formula of described tensio-active agent is:
Or
2. preparation method according to claim 1 is characterized in that, described micro-emulsion polymerization adopts thermal initiation, UV-light to cause or γShe Xianyinfajuhe.
3. the proton-exchange polymer film for preparing of claim 1.
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| CN101831023B (en) * | 2010-03-18 | 2011-07-27 | 苏州大学 | Fuel cell proton exchange membranes and preparation method thereof |
| CN104140488B (en) * | 2014-07-17 | 2016-08-17 | 中国科学院过程工程研究所 | A kind of preparation method and application of highly acid grade spherical polymeric ionic liquid resin |
| CN105817272A (en) * | 2015-08-14 | 2016-08-03 | 厦门市科宁沃特水处理科技股份有限公司 | Preparation method of anion-exchange membrane based on ion liquid polymerization |
| CN109134750B (en) * | 2018-07-20 | 2020-12-22 | 广州天思品汇实业有限公司 | Fabric aromatic material, wearing article and preparation method of fabric aromatic material |
| CN109679439A (en) * | 2018-12-27 | 2019-04-26 | 广东石油化工学院 | A kind of hydrophobicity building coating |
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