CN1557861A - Soluble sulphonated polybenzimidazole and process for preparing the same - Google Patents
Soluble sulphonated polybenzimidazole and process for preparing the same Download PDFInfo
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Abstract
Sulfonated monomer 3, 3'-disulfo-4, 4'-dicarboxyl diphenyl sulfone or its derivative, binary carboxylic acid or its derivative, 3, 4-diamino benzoic acid, and aromatic quaternary amine or its hydrochloride perform solution condensation inside phosphoric acid polymer to obtain sulfonated polybenzimidazole with controllable sulfonation degree, high molecular weight, high heat stability, high solubility good filming performance. The sulfonated polybenzimidazole may be used as film material for electric dialysis, ultrafiltering, ion exchange, proton exchange, etc. and has wide application foreground.
Description
Technical field: the present invention relates to a kind of functional high molecule material and preparation method thereof, the sulfonated polyphenyl that particularly a kind of solvability is good and imidazoles and preparation method thereof.
Background technology: Proton Exchange Membrane Fuel Cells (PEMFC) has obtained to develop rapidly at recent two decades.As one of three big critical materials of PEMFC, proton exchange membrane material has been subjected to investigator's great attention.At present, though sulfonic acid type full fluorin proton exchange film such as the commercialization of Nafion mould material because cost an arm and a leg, proton conductivity reduces and the high deficiency of methanol permeability has limited it and uses more widely under high temperature or low humidity condition.In the research and development process of novel proton exchange membranes material, more concern is placed on sulfonation special engineering plastics aspect, as sulfonated polyether ketone, sulfonated polyether-ether-ketone, sulfonated polyether sulfone, sulfonated poly thioether sulfone and sulfonated polyimide etc.
Polybenzimidazole has excellent thermostability, chemical stability and dimensional stability, is the special engineering plastics of a class excellent combination property, after last century, be developed the sixties, has been used as the matrix resin of fiber, tackiness agent, porous plastics etc.Over past ten years, caused investigator's great interest based on the acid of polybenzimidazole or the research of alkali doping proton exchange.This class doping has advantages such as excellent thermotolerance, chemical stability and chemical property and methanol permeability are low, and at high temperature with still do not have high proton conduction performance under the situation of humidification, so it is considered to be applicable to high temperature (150-200 ℃) Proton Exchange Membrane Fuel Cells and direct methanol fuel cell.Yet, from polymeric matrix, ooze out gradually with mineral acid small molecules meeting in the operational process of PEMFC of polybenzimidazole blend, therefore, the work-ing life of this type of doping is not good.
Different with the blend complex method of above-mentioned acid or alkali doping polybenzimidazole, people such as Bae (Bae J.M.; Etal.Solid State Ionics, 2002,147,189-194; Xavier Glipa; Et al.Solid State Ionics, 1997,97,323-331.) earlier with polybenzimidazole at lithium hydride and N, the effect of N-N,N-DIMETHYLACETAMIDE generates polyanion down, again with 1, and 4-butyl sultone and 1, small molecules such as 3-N-morpholinopropanesulfonic acid lactone reaction chain are respectively received the polybenzimidazole molecular backbone chain, generate side chain and have sulfonic sulfonated polyphenyl and imidazoles.This class graft type sulfonated polyphenyl and imidazoles film all have high proton conductivity under high temperature (160 ℃) or cold condition, yet adopt this grafted method, not only the time long, and the difficult control of sulfonation degree.
The another kind of method for preparing sulfonated polyphenyl and imidazoles is to adopt sulfonated aromatic dicarboxylic acid monomer and other dicarboxylic acid monomers and fragrant quaternary amine or its hydrochloride direct condensation and make.This method also is that the sulfonic acid group with proton conduction performance excellence directly is connected on the polybenzimidazole molecule of excellent combination property by chemical bond, and can effectively improve the solvability and the film-forming properties of sulfonated polyphenyl and imidazoles by the dicarboxylic acid monomer of choice structure uniqueness.So both can keep the polybenzimidazole excellent physical chemistry, can avoid again in the PEMFC operational process, moving the problem that runs off with the acid molecule of polybenzimidazole blend, can also avoid the grafting legal system and be equipped with the loaded down with trivial details technology of sulfonated polyphenyl and imidazoles, can obtain the proton exchange membrane material of long service life, proton conduction performance excellence.For example: people (Polymer Materials:Science ﹠amp such as Yoshimitsu Sakaguchi; Engineering2001,84,899; JP 2002-201268) with business-like 5-sodium sulfonate m-phthalic acid and 2-sodium sulfonate terephthalic acid as sulfonated monomers, with 3,3 '-diaminobenzidine and 3,3 ', 4,4 '-tetramino sulfobenzide has synthesized good and high sulfonated polyphenyl and the imidazoles of proton conductivity of some solubility properties as the tetramines aromatic monomer.People (Journal of Polymer Science:Part A:Polymer Chemistry 2002 such as Asensio J.A., 40,3703-3710) with 5-sodium sulfonate m-phthalic acid and 1,2,4,5-tetramino benzene has synthesized sulfonated polyphenyl that thermal stability is good and electrical property is high and imidazoles.
Summary of the invention: the present invention is from Molecular Structure Design and practical application angle, adopt the own synthetic sulfonation 4 of contriver, this class sulfonated monomers of 4 '-Dicarboxy diphenylsulfone or derivatives thereof, synthetic sulfonation degree is controlled, molecular weight is high, the sulfonated polyphenyl and the imidazoles polymkeric substance of thermostability, solvability and good film-forming property, and their repeated structural unit is as follows:
Two imino-s in the above-mentioned repeated structural unit are cis or trans; (x+z)/y=0.98-1.02 wherein, 0＜x/ (x+z)≤100%, 0≤z/ (x+z)＜100%, 10＜m＜2000.
R
1Be hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, lead or iron.
R
2Structure is by 3 of correspondence, and 4-diaminobenzoic acid, fragrant quaternary amine or its hydrochloride produce, and the difference according to the fragrant quaternary amine of selecting wherein includes a kind of or two or more R in sulfonated polyphenyl and the imidazole molecule structure
2Structure, table 1 have been enumerated some of them fragrance monomeric title of quaternary amine and corresponding R thereof
2Structure.
Table 1:R
2The title of the fragrant quaternary amine of structure and correspondence thereof
R
3Produce by the straight chain that contains 2 to 30 carbon atoms accordingly or branched fat dicarboxylic acid, aromatic dicarboxylic acids or heterocycle di-carboxylic acid, or produce by the ester class of above-mentioned di-carboxylic acid or acyl chloride derivative, wherein include a kind of or two or more R in the structural unit of sulfonated polyphenyl and imidazoles
3Structure, R
3Structure is as follows:
The method that the present invention prepares solubility sulfonated polyphenyl and imidazoles is a solution polycondensation, and concrete preparation process is as follows:
(1) reinforced mix stages, at first at 50-200 ℃ polyphosphoric acid is carried out deoxidation with rare gas element such as nitrogen or argon gas, add in this polyphosphoric acid with sulfonated monomers and di-carboxylic acid, dicarboxylic esters or binary acyl chlorides fragrant quaternary amine or its hydrochloride then and stir evenly, the ratio of the mole number sum of the mole number of above-mentioned fragrant quaternary amine or its hydrochloride and sulfonated monomers and di-carboxylic acid, dicarboxylic esters or binary acyl chlorides is between 0.98-1.02, preferably this ratio is 1, just can obtain high-molecular weight sulfonated polyphenyl and imidazoles; Monomer mass content is between 0.2-30% in this solution polymerization system;
(2) the temperature reaction stage, adopt progressively temperature-raising method, carry out polycondensation at 50-250 ℃, the reaction times is 4-400 hour, and wherein the temperature interval value is controlled at 5-60 ℃, and at each temperature spot, duration of the reaction is between 0.1-100 hour;
(3) discharging post-processing stages, after polyreaction finishes, reaction mass directly or after the dilution is poured in the precipitation agent, repetitive scrubbing is to remove solvent remaining in the product then, or with solvent remaining in alkali or the weakly alkaline inorganic salt neutralized reaction product and be washed to neutrality, final drying get final product good sulfonated polyphenyl and the imidazoles of solvability.
Synthesizing soluble sulfonated polyphenyl of the present invention and the used sulfonated monomers of imidazoles have following molecular structure:
Wherein, R
1Be hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, lead or iron, preferred R
1Be hydrogen, lithium, sodium or potassium; N is 1,2 or 3; R
4And R
5Can be identical, also can be different, R
4And R
5Can be hydroxyl, chlorine, phenoxy group or contain the straight chain or the branched alkoxyl group of 1 to 20 carbon atom, preferred R
4And R
5Be hydroxyl, chlorine or phenoxy group.
The used sulfonated monomers of synthesizing soluble sulfonated polyphenyl of the present invention and imidazoles is as 3,3 '-disulfonic acid base-4, and the preparation method of 4 '-Dicarboxy diphenylsulfone is as follows:
Fs: sulfonation stage, 4,4 '-dialkyl group sulfobenzide contacts with sulphonating agent, sulphonating agent is the vitriol oil, oleum, sulphur trioxide, chlorsulfonic acid and composition thereof, preferred sulphonating agent is an oleum, for every mole 4,4 '-dialkyl group sulfobenzide, used oleum contains the free sulphur trioxide of 2-100mol, preferred oleum contains the free sulphur trioxide of 3-12mol, and carries out sulfonation reaction under 0-200 ℃, and temperature of reaction is preferably at 70-150 ℃, reaction times is 1-12 hour, is preferably 6-10 hour;
Subordinate phase: saltout or neutralization stage, under ice-water bath or normal temperature, while stirring reaction product is slowly poured in the saturated aqueous solution such as the inorganic salt of sodium-chlor, the 0.1-300 of used oleum volume doubly when the volume of the saturated aqueous solution of these inorganic salt was sulfonation, be preferably 1-10 doubly, after leaving standstill for some time, be that the adularescent product is separated out, filter, use then such as the saturated aqueous solution of the alkali of sodium hydroxide or such as the saturated aqueous solution neutralization of the inorganic salt of yellow soda ash, crystallization is filtered to remove vitriol;
Phase III: product purification stage, add dehydrated alcohol or methyl alcohol in the filtrate after removing by filter vitriol with precipitation or crystallization, filter, filtration cakes torrefaction, can get white 4 of two the sulfonate structures that contain, the pure product of 4 '-dialkyl group sulfobenzide, this product is behind acidifying, filtration and filtration cakes torrefaction, can contain 4 of two sulfonic acid structures, 4 '-dialkyl group sulfobenzide white mass.
Quadravalence section: oxidation stage, contain 4 of two sulfonic acid structures, 4 '-dialkyl group sulfobenzide contacts with oxygenant, and oxygenant is potassium permanganate, potassium bichromate, nitric acid and oxygen, preferably use potassium permanganate and dioxygen oxidation, for the above-mentioned sulfonated products of mole, the consumption of potassium permanganate is the 4-16 mole, and the consumption of preferred potassium permanganate is the 4-6 mole, under room temperature to 170 ℃, carry out oxidizing reaction, temperature of reaction is preferably at 60-100 ℃, and the reaction times is 1-15 hour, is preferably 4-10 hour;
Five-stage: the product purification stage, with the reaction mixture filtered while hot, and with small amount of thermal water washing filter residue.Merging filtrate and washing lotion are cooled off in cooling bath, are that 10% to 36.5% hcl acidifying to congo-red test paper becomes blue with concentration then, get white needle-like crystals, the a small amount of cold water washing of suction filtration, filter cake is drained drying, get 3,3 '-disulfonic acid base-4,4 '-Dicarboxy diphenylsulfone.
The mass content of Vanadium Pentoxide in FLAKES is between 83%-89% in the polyphosphoric acid that the present invention uses.
The thinner that the present invention uses has phosphoric acid, polyphosphoric acid, methylsulfonic acid or the vitriol oil, and its quality consumption is add 0.1-200 times of polyphosphoric acid.
The precipitation agent that the present invention uses comprises water, methyl alcohol, ethanol, tetrahydrofuran (THF) or ether.
The structure of synthetic sulfonic acid type sulfonated polyphenyl of the present invention and imidazoles is confirmed through Infrared spectroscopy, and the molecular weight and the thermal stability of corresponding sodium sulfonate type sulfonated polyphenyl and imidazoles are characterized by gel chromatography (GPC) and thermogravimetry (TGA) respectively.
Advantage such as synthetic sulfonated polyphenyl of the present invention and imidazoles have that sulfonation degree is controlled, thermostability is high, solvability and film forming are good is having wide application prospect aspect the mould materials such as electrodialytic membranes, ultra-filtration membrane, ion-exchange membrane or proton exchange membrane.
Description of drawings: the infrared spectrogram of Fig. 1 sulfonated polyphenyl and imidazoles
The hot weightless picture of Fig. 2 sulfonated polyphenyl and imidazoles
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1 (preparation of sulfonated monomers): under ice-water bath, with 5 gram (0.0202mol) 4, whipping appts is equipped with in the adding of 4 '-diphenylsulfone dimethyl, in the reactor that fills the 30ml10% oleum of reflux condensing tube, violent stirring reaction at normal temperatures is after 1 hour, slowly be warming up to 90 ℃, and insulated and stirred was reacted 6 hours under this temperature, reaction solution is pale brown look, after the question response liquid cooling but, under ice-water bath, while stirring it is slowly poured in the beaker of the saturated aqueous solution that fills 120ml sodium-chlor, stir moments later, left standstill 2 hours, filter white filter cake, this white filter cake with in yellow soda ash saturated aqueous solution and after, crystallization removes by filter sodium sulfate, and adding and the isopyknic dehydrated alcohol of filtrate are with precipitation or crystallization in the filtrate, filter, filter cake can get 3 of 7.76 gram whites, 3 '-sodium disulfonate-4 80 ℃ of following vacuum-dryings 24 hours, the pure product of 4 '-diphenylsulfone dimethyl, yield is about 75%.
Accurately take by weighing 6 gram (0.0133mol) 3,3 '-sodium disulfonate-4,4 '-diphenylsulfone dimethyl add in the 250mL round-bottomed flask, add 49ml water again, load onto prolong, on the electromagnetism heating stirrer, be heated to little boiling, under agitation with sand-bath, from the prolong total amount that adds suitable for reading in batches is 10 gram potassium permanganate, add next batch again after question response is mild, the potassium permanganate of using less water (about 1ml) will stick on the prolong inwall at last pours in the bottle, continues back flow reaction after 1 hour, with the reaction mixture filtered while hot, and with small amount of thermal water washing filter residue, merging filtrate and washing lotion are cooled off in cooling bath, become blue with 25% hcl acidifying to congo-red test paper then, white needle-like crystals is separated out, a small amount of cold water washing of suction filtration, filter cake, drain, dry, get 5.5 grams 3,3 '-disulfonic acid base-4,4 '-Dicarboxy diphenylsulfone, productive rate about 82%.
Embodiment 2: agitator is being housed and nitrogen goes out; the polyphosphoric acid that adds 25 grams 84% in three mouthfuls of round-bottomed flasks of 100ml of inlet; again this round-bottomed flask is immersed in the oil bath; heating medium oil is heated to 100 ℃ and continue to stir 5 hours to remove the air in the round-bottomed flask under nitrogen protection; then in round-bottomed flask, add 1.0000 grams 3; 3 '-diaminobenzidine (4.667mmol); 0.7147 restrain 4; 4 '-Dicarboxy diphenylsulfone (2.333mmol) and 1.0884 grams 3; 3 '-disulfonic acid base-4; 4 '-Dicarboxy diphenylsulfone (2.333mmol); then under nitrogen protection and agitation condition; in 100 ℃ of reactions 5 hours; 150 ℃ were reacted 6 hours; 190 ℃ of reactions are after 5 hours; the gained viscous solution slowly poured in 1 liter of deionized water precipitate; obtain pale brown vitta shaped polymer; after being washed till slightly acidic with deionized water; use the aqueous solution soaking of yellow soda ash again; be washed to neutrality at last; in vacuum drying oven in 100 ℃ of vacuum-dryings 36 hours; can get 2.2131 gram sulfonation degree is 50% sulfonated polyphenyl and imidazoles; yield is about 99.5%; the structure of product is confirmed through Infrared spectroscopy, and its molecular weight and thermal stability are characterized by GPC and TGA respectively.
With N, dinethylformamide is made solvent, and polystyrene is a standard specimen, is 41330 in 70 ℃ of number-average molecular weights that record sodium sulfonate type sulfonated polyphenyl and imidazoles.By solution casting film forming and dilute hydrochloric acid exchange, can obtain good sulfonic acid type sulfonated polyphenyl of toughness and imidazoles film, its infrared absorpting light spectra is seen Fig. 1, therefrom can observe the following characteristics absorption band:
～3400cm
-1-N-H and-O-H stretching vibration absorption band;
3092cm
-1Fragrance-C-H stretching vibration absorption band;
1601.9cm
-1In the five-membered ring-C=N-stretching vibration absorption band;
1311.8cm
-1-SO
3O=S=O asymmetrical stretching vibration absorption band among the H;
1158.6cm
-1-SO
3O=S=O symmetrical stretching vibration absorption band among the H;
806.4cm
-1The absorption band of imidazolyl heterocycle;
693.2cm
-1-S-O stretching vibration absorption band.
This sulfonation degree is that the thermal stability of 50% sodium sulfonate type polybenzimidazole adopts TGA 2050 thermogravimetric analyzers to characterize, temperature rise rate is 20 ℃/min, nitrogen atmosphere, before beginning test in 200 ℃ of constant temperature 10min postcooling to 90 ℃, be warming up to about 850 ℃ again and test, the results are shown in Figure 2.As can be seen from Figure 2, this product has excellent thermal stability, and the temperature of its weightlessness 5% and 10% o'clock correspondence is respectively 497.1 ℃ and 528.6 ℃, and its maximum weight loss rate temperature is 514.6 ℃.
Embodiment 3: agitator is being housed and nitrogen goes out; add 25 grams, 84% polyphosphoric acid in three mouthfuls of round-bottomed flasks of 100ml of inlet; again this round-bottomed flask is immersed in the oil bath; heating medium oil is heated to 100 ℃ and continue to stir 5 hours to remove the air in the round-bottomed flask under nitrogen protection; then in round-bottomed flask, add 1.0000 grams 3; 3 '-diaminobenzidine (4.667mmol); 0.6026 restrain 4; 4 '-dicarboxyl phenyl ether (2.333mmol) and 1.0884 grams 3; 3 '-disulfonic acid base-4; 4 '-Dicarboxy diphenylsulfone (2.333mmol); then under nitrogen protection and agitation condition; in 100 ℃ of reactions 5 hours; 150 ℃ were reacted 6 hours; 190 ℃ of reactions are after 5 hours; the gained viscous solution slowly poured in 1 liter of deionized water precipitate; obtain pale brown vitta shaped polymer; after being washed till slightly acidic with deionized water; use the aqueous solution soaking of yellow soda ash again; be washed to neutrality at last; in vacuum drying oven in 100 ℃ of vacuum-dryings 36 hours; can get 2.3338 gram sulfonation degree is 50% sulfonated polyphenyl and imidazoles; yield is about 99.1%; the structure of product is confirmed through Infrared spectroscopy, and its molecular weight and thermal stability are characterized by GPC and TGA respectively.
The number-average molecular weight of synthetic sodium sulfonate type sulfonated polyphenyl and imidazoles is 35179.Can also observe characteristic absorption band in the infrared absorption spectrum of sulfonic acid type sulfonated polyphenyl and imidazoles (the solution film-forming) spectrogram as embodiment 1.
This sulfonation degree is that the thermal stability of 50% sodium sulfonate type polybenzimidazole adopts TGA 2050 thermogravimetric analyzers to characterize, testing method is with embodiment 1, the temperature of its weightlessness 5% and 10% o'clock correspondence is respectively 502.5 ℃ and 549.4 ℃, and its maximum weight loss rate temperature is 551.7 ℃.
Embodiment 4: agitator is being housed and nitrogen goes out; add 25 grams, 84% polyphosphoric acid in three mouthfuls of round-bottomed flasks of 100ml of inlet; again this round-bottomed flask is immersed in the oil bath; heating medium oil is heated to 100 ℃ and continue to stir 5 hours to remove the air in the round-bottomed flask under nitrogen protection; then in round-bottomed flask, add 1.0000 grams 3; 3 '-diaminobenzidine (4.667mmol); 0.3101 gram m-phthalic acid (1.867mmol) and 1.3060 grams 3; 3 '-disulfonic acid base-4; 4 '-Dicarboxy diphenylsulfone (2.800mmol); then under nitrogen protection and agitation condition; in 100 ℃ of reactions 5 hours; 150 ℃ were reacted 6 hours; 190 ℃ of reactions are after 5 hours; the gained viscous solution slowly poured in 1 liter of deionized water precipitate; obtain pale brown vitta shaped polymer; after being washed till slightly acidic with deionized water; use the aqueous solution soaking of yellow soda ash again; be washed to neutrality at last; in vacuum drying oven in 100 ℃ of vacuum-dryings 36 hours; can get 2.2595 gram sulfonation degree is 60% sulfonated polyphenyl and imidazoles; yield is about 99.1%; the structure of product is confirmed through Infrared spectroscopy, and its molecular weight and thermal stability are characterized by GPC and TGA respectively.
The number-average molecular weight of synthetic sodium sulfonate type sulfonated polyphenyl and imidazoles is 38430.Can also observe characteristic absorption band in the infrared absorption spectrum of sulfonic acid type sulfonated polyphenyl and imidazoles (the solution film-forming) spectrogram as embodiment 1.
This sulfonation degree is that the thermal stability of 60% sodium sulfonate type polybenzimidazole also adopts TGA 2050 thermogravimetric analyzers to characterize, testing method is with embodiment 1, the temperature of its weightlessness 5% and 10% o'clock correspondence is respectively 515.4 ℃ and 551.5 ℃, and its maximum weight loss rate temperature is about 554.6 ℃.
Claims (6)
1. solubility sulfonated polyphenyl and imidazoles is characterized in that having following repeated structural unit:
Two imino-s in the above-mentioned repeated structural unit are cis or trans; (x+z)/y=0.98-1.02 wherein, 0＜x/ (x+z)≤100%, 0≤z/ (x+z)＜100%, 10＜m＜2000;
R
1Be hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, lead or iron;
R
2Structure is as follows:
Wherein include a kind of or two or more R in the structural unit of sulfonated polyphenyl and imidazoles
2Structure;
R
3Structure is as follows:
Wherein: x=H, Cl, F, Br or I, n=0～28;
The ortho position, a position or contraposition;
2,2 ' position, 3,3 ' position or 4,4 ' position, wherein: Y=-, O, S, SO
2, CO, CH
2, C (CH
3)
2Or C (CF
3)
2:
Wherein include a kind of or two or more R in the structural unit of sulfonated polyphenyl and imidazoles
3Structure.
2. the preparation method of solubility sulfonated polyphenyl and imidazoles is characterized in that adopting the method for solution polycondensation, and concrete preparation process is as follows:
(1) reinforced mix stages, at first at 50-200 ℃ polyphosphoric acid is carried out deoxidation with rare gas element such as nitrogen or argon gas, add in this polyphosphoric acid with sulfonated monomers and di-carboxylic acid, dicarboxylic esters or binary acyl chlorides fragrant quaternary amine or its hydrochloride then and stir evenly, the ratio of the mole number sum of the mole number of above-mentioned fragrant quaternary amine or its hydrochloride and sulfonated monomers and di-carboxylic acid, dicarboxylic esters or binary acyl chlorides is between 0.98-1.02, and monomer mass content is between 0.2-30% in this solution polymerization system;
(2) the temperature reaction stage, adopt progressively temperature-raising method, carry out polycondensation at 50-250 ℃, the reaction times is 4-400 hour, and wherein the temperature interval value is controlled at 5-60 ℃, and at each temperature spot, duration of the reaction is between 0.1-100 hour;
(3) discharging post-processing stages, after polyreaction finishes, reaction mass directly or after the dilution is poured in the precipitation agent, repetitive scrubbing is to remove solvent remaining in the product then, or with solvent remaining in alkali or the weakly alkaline inorganic salt neutralized reaction product and be washed to neutrality, final drying get final product good sulfonated polyphenyl and the imidazoles of solvability.
3. the preparation method of solubility sulfonated polyphenyl according to claim 2 and imidazoles is characterized in that employed sulfonated monomers has following molecular structure:
Wherein, R
1Be hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, lead or iron; N is 1,2 or 3; R
4And R
5Can be identical, also can be different, R
4And R
5Comprise hydroxyl, chlorine, phenoxy group or contain the straight chain or the branched alkoxyl group of 1 to 20 carbon atom.
4. the preparation method of solubility sulfonated polyphenyl according to claim 2 and imidazoles, the mass content that it is characterized in that Vanadium Pentoxide in FLAKES in the polyphosphoric acid is between 83%-89%.
5. the preparation method of solubility sulfonated polyphenyl according to claim 2 and imidazoles is characterized in that thinner has phosphoric acid, polyphosphoric acid, methylsulfonic acid or the vitriol oil, and its quality consumption is the 0.1-200 times of add polyphosphoric acid.
6. the preparation method of solubility sulfonated polyphenyl according to claim 2 and imidazoles, its feature comprises water, methyl alcohol, ethanol, tetrahydrofuran (THF) or ether at precipitation agent.
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| CN102127240B (en) * | 2010-12-15 | 2012-10-31 | 上海交通大学 | Blend film of sulfonated poly(arylene ether) or thioether containing triphenylphosphine oxide and sulfonated polybenzimidazole and preparation method thereof |
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| CN102881853B (en) * | 2012-09-17 | 2015-03-25 | 中国科学院金属研究所 | Blending membrane for all-vanadium redox flow battery and preparation method for blending membrane |
| CN113773491A (en) * | 2021-08-11 | 2021-12-10 | 华南师范大学 | Polybenzimidazole derivative and application thereof in field of fluorescent probes |
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| CN115746560A (en) * | 2022-10-20 | 2023-03-07 | 北京和瑞储能科技有限公司 | Amphiphilic alcohol self-assembly induced sulfonated polybenzimidazole ion exchange composite membrane and preparation method thereof |
| CN115746560B (en) * | 2022-10-20 | 2024-02-09 | 北京和瑞储能科技有限公司 | Amphiphilic alcohol self-assembly induced sulfonated polybenzimidazole ion exchange composite membrane and preparation method thereof |
| CN116284779A (en) * | 2023-04-23 | 2023-06-23 | 武汉恒志新型材料科技有限公司 | Synthesis method of polybenzimidazole polymer |
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