CN103086999B - Novel fluorine-containing polybenzimidazole polymer, fluorinated organic diacid monomer as intermediate of the fluorine-containing polybenzimidazole polymer, and their preparation method - Google Patents
Novel fluorine-containing polybenzimidazole polymer, fluorinated organic diacid monomer as intermediate of the fluorine-containing polybenzimidazole polymer, and their preparation method Download PDFInfo
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Abstract
The invention discloses a fluorine-containing polybenzimidazole polymer, a fluorinated organic diacid monomer as an intermediate of the fluorine-containing polybenzimidazole polymer, and their preparation method. The novel fluorine-containing polybenzimidazole polymer is shown in a structural formula 4. The fluorinated organic diacid is shown in a structural formula 3. The preparation method comprises the following steps that methyl-substituted fluorine-containing benzoic acid and hydrazine hydrate undergo a condensation reaction in polyphosphoric acid to produce fluorinated oxadiazolene xylene; the fluorinated oxadiazolene xylene as an intermediate is oxidized into a fluorinated organic diacid monomer by potassium permanganate or nitric acid; and the fluorinated organic diacid monomer, a composite diacid monomer and a tetramine monomer undergo a polycondensation reaction in polyphosphoric acid to produce the novel fluorine-containing polybenzimidazole polymer. The fluorine-containing polybenzimidazole polymer has good solubility and oxidation-resistant stability and can be used as a high-temperature proton exchange membrane, a separating membrane, a sensor, a high temperature-resistant fiber, a composite material, a binder and other function material for a fuel cell.
Description
Technical field
The invention belongs to functional high molecule material preparing technical field, be specifically related to a kind of fluorine-containing polybenzimidazole polymer and intermediate fluoro organic diacid thereof and their preparation method and application.
Background technology
Fuel cell, as novel generation generation technology, receives people's concern day by day with its green, efficient feature.The outstanding representative in fuel cell using high score proton exchange membrane as electrolytical Proton Exchange Membrane Fuel Cells (PEMFC), its advantage be simple in structure, energy efficiency is high, environmental friendliness zero release, can started quickly at low temperature etc., represented wide application prospect at aspects such as automobile power power supply, distributed small-sized supply stations, national governments and large enterprises invariably to input huge fund research and develop.The core material of PEMFC is proton exchange membrane, is also polymer dielectric film, plays the effect of transmission proton, obstruct fuel and air in battery.Unique commercial proton exchange membrane is perfluoro sulfonic acid membrane at present, it has high proton conductivity, good chemically stable, shortcoming is that cost is high, use temperature low (80 DEG C or following), it is poisoning that lower temperature operation condition faces such as Catalyst for CO fuel cell in the time of practical application, many problems such as the hydro-thermal difficult management of system and the recovery utilization rate of heat energy are low, cause fuel cell generation heat radiation difficulty, complex structure and the low inferior practical problems of total energy effect, and to improve the operating temperature of PEMFC, must development of new high-temperature resistant proton exchange membrane material.Polybenzimidazole is because second-order transition temperature is high, after the mineral acid doping such as phosphoric acid, can realize compared with the proton conduction under anhydrous condition and comparatively high temps, is considered to high-temperature resistant proton exchange membrane ideal material.But in the empty PEMFC battery operation of hydrogen, must consider the resistance to oxidation stability of film, this is the H generating due in PEMFC cathode electrode reaction process
2o
2and-OH or/and-molecular chain of OOH free radical in can degraded films, cause the oxidative degradation of film.Because polybenzimidazole main chain is carbon-carbon bond and hydrocarbon key, its resistance to oxidation stability need further raising compared with perfluoro sulfonic acid membrane.Meanwhile, traditional polybenzimidazole material because of its molecular chain rigid structure and Intermolecular Forces strong, cause this class material dissolves poor performance.Masking difficulty, therefore, improves by molecular designing, and the dissolving processing characteristics and the oxidation resistent susceptibility that improve polybenzimidazole are that this class material obtains the further key point of application.
In sum, although polybenzimidazole material has a series of excellent properties, if can obtain application in PEMFC, must improve it and dissolve processing characteristics and resistance to oxidation stability.
Summary of the invention
The novel fluorine polybenzimidazole polymer material that the object of this invention is to provide a kind of fluoro organic diacid and prepare taking it as monomer.
Fluoro organic diacid provided by the present invention, its general structure as shown in Equation 3:
Substituent X 1, X2, X3, X4 in described formula 3 on Ar are H or F, and wherein at least one is F, and preferably at least two substituting groups are F.
Fluorine-containing polybenzimidazole polymer provided by the present invention, its general structure as shown in Equation 4:
In described formula 4, n: m=(1000-0): (0-1000), and m is not that 0, n equals or is not equal to 0.
In the time of n ≠ 0, n: m=(0.1-1): (0.1-1), preferably n: m=(0.3-0.9): (0.3-0.9) or n: m=(0.2-0.8): (0.2-0.8); Concrete n: m can be 0.2: 0.8,0.3: 0.7,0.4: 0.6,0.5: 0.5,0.6: 0.4,0.7: 0.3.
In described formula 4, Ar in the definition cotype 3 of Ar;
Above-mentioned fluorine-containing polybenzimidazole polymer can form random copolymers, segmented copolymer or alternating copolymer by two portions repeated structural unit shown in formula 4.
The number-average molecular weight of this polymkeric substance is 1 × 10
4-20 × 10
4, specifically can be 1 × 10
4-10 × 10
4, 5 × 10
4-15 × 10
4or 8 × 10
4-20 × 10
4, preferably 8 × 10
4-10 × 10
4.
The as directed fluoro organic acid of above-mentioned formula 3 general structure, its chemosynthesis step as shown in Figure 1.
Its preparation method, specifically comprises the steps:
1) under inert atmosphere protection, fluorinated organic compound, hydrazine hydrate and polyphosphoric acid (PPA) shown in formula 1 are mixed to post-heating and make reactants dissolved to 50-80 DEG C, and then be warming up to 120-200 DEG C and react, reaction finish after by reaction mixture impouring deionized water, filter collecting precipitation, gained is precipitated through soda lye wash, obtain compound shown in formula 2;
2) compound shown in formula 2 and oxygenant are carried out to oxidizing reaction, obtain the compound of fluoro organic diacid shown in formula 3;
Wherein, the Ar in the definition cotype 3 of the Ar in formula 1 and formula 2.
Above-mentioned steps 1) in, the molfraction of the fluorinated organic compound shown in formula 1, hydrazine hydrate, PPA is than being (2-2.2): 1: (5-20), and preferably 2.1: 1: 15; Described inert atmosphere is nitrogen or argon gas atmosphere; The reaction times of described reaction is 8-24 hour, preferably 15 hours.
Step 2) in, oxidizing reaction oxygenant used is potassium permanganate; Compound shown in described formula 2 is 1 with the molfraction ratio of described oxygenant: 3-10, preferably 1: 4; The reaction solvent of described oxidizing reaction is the mixed solvent of water and pyridine, and wherein, water and pyridine mass ratio are 1: (0.5-2.5), preferably 1: 1, the temperature of reaction of oxidizing reaction was reflux temperature, and the reaction times is 2-100 hour, preferably 20 hours.
The as directed fluorine-containing polybenzimidazole polymer of above-mentioned formula 4 general structure, its chemosynthesis step as shown in Figure 2.
Its preparation method, specifically comprises the steps:
Under inert atmosphere protection; described fluoro organic diacid compound, compound diacid monomer, tetramine monomers and polyphosphoric acid (PPA) are mixed; first react at 60-80 DEG C; being warming up to 120-140 DEG C reacts again; finally be warming up to 160-250 DEG C and react, obtain the solution of described fluorine-containing polybenzimidazole polymer.
In the method, described compound diacid monomer is for telomerized polymer segment rigidity and solubility property, specifically be selected from m-phthalic acid, terephthalic acid, 2, 6 dicarboxyl pyridines, 3, 5 dicarboxyl pyridines, 1, two (the 4-carboxyl)-phenoxy group-benzene of 4-, 1, two (the 4-carboxyl)-phenoxy group-benzene of 3-, 1, two (the 3-carboxyl)-phenoxy group-benzene of 3-, 1, two (the 3-carboxyl)-phenoxy group-benzene of 4-, 5-(3, 5-trifluoromethyl-phenoxy group)-m-phthalic acid, 1, 2-bis trifluoromethyl-3, at least one in two ((the 4-carboxyl)-phenyl) methane of 4-and 5-sodium sulfonate group-m-phthalic acid.
Described tetramine monomers is selected from 3, and 3 ', 4,4 '-tetramine yl diphenyl ether, 3,3 ', 4,4 '-tetramine base biphenyl, 1,2,4,5-tetramine base benzene, 3,3 ', 4,4 '-tetra-aminobenzophenones, 3,3 ', 4,4 '-tetramine base sulfobenzide and 1,2-dimethyl-3, at least one in two (4-(3,4-, the bis-amido benzene oxygen)-benzene) methylmethanes of 4-.
The mol ratio of described fluoro organic diacid compound, compound diacid monomer, tetramine monomers is x: (1-x): 1, and wherein x=0-1 but do not comprise 0; Organic diacid compound, compound diacid monomer and the total amount of tetramine monomers and the ratio of quality and the number of copies of polyphosphoric acid are 100: 300-4000, specifically can be 100: 390-3900,100: 380-3800,100: 350-3500,100: 400-3000,100: 500-2500,100: 1000-3000 or 100: 2500-3000.
60-80 DEG C of time of reacting is 2-8 hour, and 120-140 DEG C of time of reacting is 4-6 hour, and 160-250 DEG C of time of reacting is 12-24 hour.
After completion of the reaction, also can be handled as follows reaction system: fluorine-containing polybenzimidazole solution is cooled and is placed in large water gaging, obtain polymkeric substance precipitation, the NaHCO that is 1-10% by a large amount of mass concentrations by this polymkeric substance precipitation
3or Na
2cO
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, and collecting precipitation is also dry, obtains fluorine-containing polybenzimidazole polymer (resin).
Above-mentioned fluorine-containing polybenzimidazole polymer, in the application of preparing in polybenzimidazole film, polybenzimidazole/phosphoric acid composite proton exchange membrane material, separatory membrane, sensor, high-temperature fibre, high temperature resistant composite and binding agent, also belongs to protection scope of the present invention.
Wherein, described fluorine-containing polybenzimidazole film can be prepared according to the ordinary method comprising the steps: described fluorine-containing polybenzimidazole polymer and organic solvent are mixed, after back flow reaction, obtain the preparation liquid of fluorine-containing polybenzimidazole polymer, described preparation liquid is coated to carrier and be placed in baking oven through thermal treatment masking, cooling and demolding obtains described fluorine-containing polybenzimidazole film.
Wherein, described organic solvent is selected from N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, at least one in N '-dimethyl formamide, meta-cresol, p-cresol, dimethyl sulfoxide (DMSO), gamma-butyrolactone, sulfobenzide and tetramethylene sulfone.
The ratio of quality and the number of copies of described fluorine-containing polybenzimidazole polymer and organic solvent is 10: 100-200.
Described heat treatment step comprises successively: at 60 DEG C of thermal treatment 6-16 hours, 80 DEG C thermal treatment 2-8 hour, 120 DEG C thermal treatment 1-6 hour and 180 DEG C of thermal treatment 10-16 hour.
Described fluorine-containing polybenzimidazole/phosphoric acid composite proton exchange membrane material, can be prepared according to the ordinary method comprising the steps: 1) described fluorine-containing polybenzimidazole polymer and organic solvent are mixed, after back flow reaction, obtain the preparation liquid of polybenzimidazole polymer, described preparation liquid is coated to carrier and be placed in baking oven through thermal treatment masking, cooling demoulding obtains fluorine-containing polybenzimidazole film;
2) described fluorine-containing polybenzimidazole film is soaked in phosphate aqueous solution, after taking-up, cleans with deionized water rapidly, obtain described polybenzimidazole/phosphoric acid composite proton exchange membrane material.
Wherein, described organic solvent is selected from N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, at least one in N '-dimethyl formamide, meta-cresol, p-cresol, dimethyl sulfoxide (DMSO), gamma-butyrolactone, sulfobenzide and tetramethylene sulfone; Described heat treatment step comprises successively: at 60 DEG C of thermal treatment 6-16 hours, 80 DEG C thermal treatment 2-8 hour, 120 DEG C thermal treatment 1-6 hour and 180 DEG C of thermal treatment 10-16 hour; Describedly state polybenzimidazole polymer, described organic solvent ratio of quality and the number of copies is 10: 100-200; Described phosphate aqueous solution mass percentage concentration is 50-90%, and the time of described soaking step is 5-10 days.
The present invention, by introducing containing fluorine structure in polybenzimidazole molecule, to reduce the Intermolecular Forces of macromolecular chain, has significantly improved polybenzimidazole solubility property; Meanwhile, the introducing of fluoro-containing group, has given polybenzimidazole more excellent oxidation resistent susceptibility.
The method of preparing fluoro organic diacid provided by the invention, has the advantages that raw material is easy to get, synthetic route succinct, be suitable for scale operation.The polybenzimidazole resin providing can be dissolved in conventional organic solvent under condition of normal pressure, solubleness can reach 3-11%, has good resistance toheat, and its second-order transition temperature reaches 282-366 DEG C, antioxidant property excellence in fuel cell, can reach 3000-9000 hour work-ing life.Can be used for preparing high temperature proton exchange film for fuel cell, sensor, high-temperature fibre, matrix material, binding agent and other functional materialss, there is important using value.
Brief description of the drawings
Fig. 1 is the chemical reaction flow process figure of fluoro organic diacid shown in preparation formula 3 of the present invention.
Fig. 2 is the chemical reaction flow process figure of fluorine-containing polybenzimidazole polymer shown in preparation formula 4 of the present invention.
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of organic diacid shown in the formula 3 (X2=F, X3=F) prepared of the present invention
Fig. 4 is the infrared spectrum of organic diacid shown in the formula 3 (X2=F, X3=F) prepared of the present invention.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1,
1) prepare fluoro organic diacid monomer
At N
2under protection, in there-necked flask, add 2; the fluoro-4 tolyl acid 172g of 3-bis-; hydrazine hydrate 25g; polyphosphoric acid 750g (three's mol ratio is 2: 1: 15); open and stir; slowly be heated to 60 reaction 3h; be warming up to 120 DEG C of reaction 8h, by reaction mixture impouring 5L water, filter and collect white precipitate; to precipitate with in the mass concentration 1%NaOH aqueous solution and after; be washed to neutrality, vacuum-drying, obtains 182g white intermediate 2; two (fluoro-4 methylbenzene of 2, the 3-bis-) oxadiazoles of 5-.Getting this intermediate 32.2g (0.1mol) adds in 2L there-necked flask, then add water 40g, pyridine 100g, is heated to reflux, and slowly gradation adds potassium permanganate to add 47.4g (0.3mol), back flow reaction 100h, by in excessive reactant impouring mass concentration 10% hydrochloric acid, filter collecting precipitation, by throw out with obtaining 28g 2 after ethyl alcohol recrystallization vacuum-drying, two (the fluoro-4 carboxyl benzene of 2, the 3-bis-) oxadiazoles of 5-.Its nucleus magnetic hydrogen spectrum figure is shown in Fig. 3, and infrared spectrum is shown in Fig. 4.
2) prepare fluorine-containing polybenzimidazole polymer
Under nitrogen protection; by 2 of 38.2g; 5-two (2; the fluoro-4 carboxyl benzene of 3-bis-) oxadiazole; 24.6g 5-sodium sulfonate-m-phthalic acid, 46g 3,3 '; 4,4 '-tetramine yl diphenyl ether (above-mentioned three's mol ratio is 0.5: 0.5: 1) adds in 450g polyphosphoric acid and is uniformly mixed.Said mixture is slowly heated to 60 DEG C of reactions 4 hours, and 120 DEG C are reacted 4 hours, and 180 DEG C of reactions obtained polybenzimidazole solution after 12 hours.After being cooled, this solution in impouring 2.5 premium on currency, obtains polymkeric substance precipitation, the NaHCO that is 1% by a large amount of mass concentrations by this precipitation
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, collecting precipitation dry 125g polybenzimidazole resin (PBI-1, the m in counter structure formula 4: n=0.5: 0.5), the number-average molecular weight of this resin is 8.1 × 10 of obtaining
4(adopting GPC to measure, taking DMSO as moving phase).The physical and chemical performance of this resin is as shown in table 1.
Get gained polybenzimidazole 10g, add 300mL dimethyl sulfoxide (DMSO), be heated with stirring to and reflux 8 hours, obtain homogeneous polymer solution.By appropriate above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, being placed in baking oven heat-treats, concrete steps are as follows: 60 DEG C 6 hours, 80 DEG C 2 hours, 120 DEG C 2 hours, 180 DEG C 10 hours, be cooled to room temperature, after demoulding, obtain polybenzimidazole film, the performance of this film is as shown in table 2.
Above-mentioned film is soaked in mass concentration 50% phosphoric acid solution to 10 days, after taking-up, rinse out surface acid solution with deionized water rapidly, and sop up surface-moisture with filter paper, and obtaining polybenzimidazole/phosphoric acid composite proton exchange membrane material, the performance of this material is as shown in table 2.
Embodiment 2,
1) prepare fluoro organic diacid monomer
At N
2under protection, in there-necked flask, add 2; 3,5,6-tetrafluoro-4-tolyl acid 114g; one hydrazine hydrate 12.5g; polyphosphoric acid 380g (three's mol ratio is 2.2: 1: 15), opens and stirs, and is slowly heated to 80 DEG C of reaction 3h; be warming up to 200 DEG C of reaction 24h; by in reaction mixture impouring 3L water, filter collect white precipitate, by gained throw out with mass concentration 1%Na
2cO
3in the aqueous solution and after, be washed to neutrality, vacuum-drying, obtains 116g white intermediate 2, two (2,3,5, the 6-tetrafluoro-4 methylbenzene) oxadiazoles of 5-.Gained intermediate is got to 39.4g (0.1mol) and add in 2L there-necked flask, then add water 100g, pyridine 100g, be heated to reflux, slowly gradation adds potassium permanganate to add 63g (0.4mol), and back flow reaction 20h, by excessive reactant impouring mass concentration 10% hydrochloric acid, filter collecting precipitation, by throw out with obtaining 36g 2 after ethyl alcohol recrystallization vacuum-drying, 5-two (2,3,5,6-tetrafluoro-4 carboxyl benzene) oxadiazole.
2) prepare fluorine-containing polybenzimidazole polymer
Under argon shield; by 2 of 9.8g; 5-two (2,3,5; 6-tetrafluoro-4 carboxyl-benzene) oxadiazole; 1.32g m-phthalic acid, 2.3g 3,3 '; 4,4 '-tetramine yl diphenyl ether (above-mentioned three's mol ratio is 0.2: 0.8: 1) adds in 120g polyphosphoric acid and is uniformly mixed.Said mixture is slowly heated to 60 DEG C of reactions 8 hours, and 120 DEG C are reacted 4 hours, and 250 DEG C of reactions obtained polybenzimidazole solution after 24 hours.After being cooled, this solution in impouring 4L water, obtains polymkeric substance precipitation, the NaHCO that is 5% by a large amount of mass concentrations by this polymkeric substance precipitation
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, collecting precipitation dry 13.1g polybenzimidazole resin (PBI-2, the m in counter structure formula 4: n=0.2: 0.8), the number-average molecular weight of this resin is 15 × 10 of obtaining
4.The physical and chemical performance of this resin is as shown in table 1.
Get gained polybenzimidazole 10g, add 300mL dimethyl sulfoxide (DMSO) (DMSO), be heated with stirring to and reflux 10 hours, obtain homogeneous polymer solution.Appropriate above-mentioned polymkeric substance preparation liquid curtain coating, on clean sheet glass or other carriers, is placed in to 60 DEG C of baking oven thermal treatments 12 hours, 80 DEG C 6 hours, 120 DEG C 6 hours, 180 DEG C 12 hours, be cooled to room temperature, after demoulding, obtain polybenzimidazole film, the performance of this film is as shown in table 2.
Above-mentioned film is soaked in mass concentration 60% phosphoric acid solution to 9 days, after taking-up, rinse out surface acid solution with deionized water rapidly, and sop up surface-moisture with filter paper, and obtaining polybenzimidazole/phosphoric acid composite proton exchange membrane material, the performance of this material is as shown in table 2.
Embodiment 3,
1) prepare fluoro organic diacid monomer
Under argon shield, in there-necked flask, add 2; 3,4,6-tetrafluoro-5-tolyl acid 218g; one hydrazine hydrate 25g; polyphosphoric acid 260g (three's mol ratio is 2.1: 1: 5), opens and stirs, and is slowly heated to 80 DEG C of reaction 4h; be warming up to 200 DEG C of reaction 16h; by in reaction mixture impouring 3L water, filter collecting precipitation, by gained throw out with mass concentration 1%Na
2cO
3in the aqueous solution and after wash with water to neutrality, vacuum-drying obtains 197g white intermediate (2,3,4,6-tetrafluoro-5-methylbenzene) oxadiazole.Get this intermediate 39.4g (0.1mol) and add in 2L there-necked flask, then add water 120g, pyridine 60g, be heated to reflux, slowly gradation adds potassium permanganate to add 158g (1.0mol), and back flow reaction 2h, by excessive reactant impouring mass concentration 10% hydrochloric acid, filter collecting precipitation, by throw out with obtaining 32g 2 after methanol/water recrystallization vacuum-drying, 5-two (2,3,4,6-tetrafluoro-5-carboxyl benzene) oxadiazole.
2) prepare fluorine-containing polybenzimidazole polymer
Under nitrogen protection, by 2 of 22.7g, 5-two (2,3; 4,6-tetrafluoro-5-carboxyl benzene) oxadiazole, 10.7g 3; 3 ', 4,4 '-tetramine base biphenyl (said two devices mol ratio is 1: 1) adds in 400g polyphosphoric acid and is uniformly mixed.Said mixture is slowly heated to 80 DEG C of reactions 2 hours, and 130 DEG C are reacted 4 hours, and 210 DEG C of reactions obtained polybenzimidazole solution after 20 hours.After being cooled, this solution in a large amount of water of impouring, obtains polymkeric substance precipitation, the Na that is 2% by a large amount of mass concentrations by this polymkeric substance precipitation
2cO
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, and collecting precipitation also dryly obtains 32g polybenzimidazole resin (PBI-3, m=1, n=0 in counter structure formula 4), and the number-average molecular weight of this resin is 9.5 × 10
4.The physical and chemical performance of this resin is as shown in table 1.
Get gained polybenzimidazole 10g, add 250mL dimethyl sulfoxide (DMSO), be heated with stirring to and reflux 12 hours, obtain homogeneous polymer solution.Appropriate above-mentioned polymkeric substance preparation liquid curtain coating, on clean sheet glass or other carriers, is placed in to 60 DEG C of baking oven thermal treatments 16 hours, 80 DEG C 4 hours, 120 DEG C 6 hours, 180 DEG C 16 hours, be cooled to room temperature, after demoulding, obtain polybenzimidazole film, the performance of this film is as shown in table 2.
Above-mentioned film is soaked in mass concentration 85% phosphoric acid solution to 6 days, after taking-up, rinse out surface acid solution with deionized water rapidly, and sop up surface-moisture with filter paper, and obtaining polybenzimidazole/phosphoric acid composite proton exchange membrane material, the performance of this material is as shown in table 2.
Embodiment 4,
1) prepare fluoro organic diacid monomer
Under N2 protection, in there-necked flask, add 2; the fluoro-5 tolyl acid 86g of 3-bis-; one hydrazine hydrate 12.5g; polyphosphoric acid 990g (three's mol ratio is 2: 1: 20); open and stir; slowly be heated to 70 DEG C of reaction 5h; be warming up to 120 DEG C of reaction 10h; by in reaction mixture impouring 3L water; filter collecting precipitation, by gained throw out with in the mass concentration 4%NaOH aqueous solution and after wash with water to neutrality, vacuum-drying obtains 90g white intermediate 2; two (the fluoro-5-methylbenzene of 2, the 3-bis-) oxadiazoles of 5-.
Getting above-mentioned intermediate 66.4g (0.2mol) adds in 4L there-necked flask, then add water 200g, pyridine 250g, is heated to reflux, and slowly gradation adds potassium permanganate to add 188.8g (1.2mol), back flow reaction 72h, by in excessive reactant impouring mass concentration 10% hydrochloric acid, filter collecting precipitation, by throw out with obtaining 63g 2 after ethanol/water recrystallization vacuum-drying, two (the fluoro-5-carboxyl of 2, the 3-bis-benzene) oxadiazoles of 5-.
2) prepare fluorine-containing polybenzimidazole polymer
Under nitrogen protection; by 2 of 22.9g; 5-two (2; the fluoro-5-carboxyl of 3-bis-benzene) oxadiazole; 6.7g 2,6 dicarboxyl pyridine and 27.8g3,3 '; 4,4 '-tetramine base sulfobenzide (above-mentioned three's mol ratio is 0.6: 0.4: 1) adds in 800g polyphosphoric acid and is uniformly mixed.Said mixture is slowly heated to 60 DEG C of reactions 6 hours, and 120 DEG C are reacted 6 hours, and 220 DEG C of reactions obtained polybenzimidazole solution after 24 hours.After being cooled, this solution in impouring 12 premium on currency, obtains polymkeric substance precipitation, the NaHCO that is 10% by a large amount of mass concentrations by this polymkeric substance precipitation
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, collecting precipitation dry 56g polybenzimidazole resin (PBI-4, the m in counter structure formula 4: n=0.6: 0.4), the number-average molecular weight of this resin is 8.1 × 10 of obtaining
4.The physical and chemical performance of this resin is as shown in table 1.
Get gained polybenzimidazole 10g, add 200mL N,N-DIMETHYLACETAMIDE (DMAC), be heated with stirring to and reflux 6 hours, obtain homogeneous polymer solution.Appropriate above-mentioned polymkeric substance preparation liquid curtain coating, on clean sheet glass or other carriers, is placed in to 60 DEG C of baking oven thermal treatments 6 hours, 80 DEG C 4 hours, 120 DEG C 4 hours, 180 DEG C 14 hours, be cooled to room temperature, after demoulding, obtain polybenzimidazole film, the performance of this film is as shown in table 2.
Above-mentioned film is soaked in mass concentration 70% phosphoric acid solution to 7 days, after taking-up, rinse out surface acid solution with deionized water rapidly, and sop up surface-moisture with filter paper, and obtaining polybenzimidazole/phosphoric acid composite proton exchange membrane material, the performance of this material is as shown in table 2.
Embodiment 5,
Under argon shield; prepared by the embodiment of 26.7g 42; 5-two (2; the fluoro-5-carboxyl of 3-bis-benzene) oxadiazole; 7.74g 1, two (3-carboxyl)-phenoxy group-benzene and the 23g3 of 3-, 3 '; 4,4 '-tetramine yl diphenyl ether (above-mentioned three's mol ratio is 0.7: 0.3: 1) adds in 800g polyphosphoric acid and is uniformly mixed.Said mixture is slowly heated to 80 DEG C of reactions 4 hours, and 140 DEG C are reacted 6 hours, and 200 DEG C of reactions obtained polybenzimidazole solution after 16 hours.After being cooled, this solution in impouring 6 premium on currency, obtains polymkeric substance precipitation, the Na that is 3% by a large amount of mass concentrations by this polymkeric substance
2cO
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, collecting precipitation dry polybenzimidazole resin (PBI-5, the m in counter structure formula 4: n=0.7: 0.3), the number-average molecular weight of this resin is 7.7 × 10 of obtaining
4.The physical and chemical performance of this resin is as shown in table 1.
Get gained polybenzimidazole 10g, add 200mLN-methyl-2-pyrrolidone (NMP), be heated with stirring to and reflux 5 hours, obtain homogeneous polymer solution.Appropriate above-mentioned polymkeric substance preparation liquid curtain coating, on clean sheet glass or other carriers, is placed in to 60 DEG C of baking oven thermal treatments 12 hours, 80 DEG C 8 hours, 120 DEG C 5 hours, 180 DEG C 15 hours, be cooled to room temperature, after demoulding, obtain polybenzimidazole film, the performance of this film is as shown in table 2.
Above-mentioned film is soaked in mass concentration 80% phosphoric acid solution to 7 days, take out, rinse out surface acid solution with deionized water rapidly, and sop up surface-moisture with filter paper, obtain polybenzimidazole/phosphoric acid composite proton exchange membrane material, the performance of this material is as shown in table 2.
Embodiment 6,
Under argon shield; prepared by 27.2g embodiment 32,5-two (2,3; 4; 6-tetrafluoro-5-carboxyl benzene) oxadiazole, 49.1g Isosorbide-5-Nitrae-bis-(3-carboxyl)-phenoxy group-benzene and 88.2g 1; 2-dimethyl-3; two (4-(3,4-, the bis-amido benzene oxygen)-benzene) methylmethanes (above-mentioned three's mol ratio is 0.3: 0.7: 1) of 4-, add in 2500g polyphosphoric acid and are uniformly mixed.Said mixture is slowly heated to 60 DEG C of reactions 6 hours, and 140 DEG C are reacted 6 hours, and 250 DEG C of reactions obtained polybenzimidazole solution after 24 hours.After being cooled, this solution in impouring 20L water, obtains polymkeric substance precipitation, the Na that is 10% by a large amount of mass concentrations by this polymkeric substance
2cO
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, collecting precipitation dry polybenzimidazole resin (PBI-6, the m in counter structure formula 4: n=0.3: 0.7), the number-average molecular weight of this resin is 9.5 × 10 of obtaining
4.The physical and chemical performance of this resin is as shown in table 1.
Get gained polybenzimidazole 30g, add 450mL dimethyl formamide DMF, be heated with stirring to and reflux 4 hours, obtain homogeneous polymer solution.Appropriate above-mentioned polymkeric substance preparation liquid curtain coating, on clean sheet glass or other carriers, is placed in to 60 DEG C of baking oven thermal treatments 16 hours, 80 DEG C 6 hours, 120 DEG C 6 hours, 180 DEG C 12 hours, be cooled to room temperature, after demoulding, obtain polybenzimidazole film, the performance of this film is as shown in table 2.
Above-mentioned film is soaked in mass concentration 85% phosphoric acid solution to 6 days, take out, rinse out surface acid solution with deionized water rapidly, and sop up surface-moisture with filter paper, obtain polybenzimidazole/phosphoric acid composite proton exchange membrane material, the performance of this material is as shown in table 2.
Embodiment 7,
Under argon shield; prepared by 19.1g embodiment 42; 5-two (2; the fluoro-5-carboxyl of 3-bis-benzene) oxadiazole; 13.5g 5-sodium sulfonate group-m-phthalic acid and 27.8g 3,3 ', 4; 4 '-tetramine base sulfobenzide (above-mentioned three's mol ratio is 0.5: 0.5: 1), adds in 600g polyphosphoric acid and is uniformly mixed.Said mixture is slowly heated to 80 DEG C of reactions 5 hours, and 130 DEG C are reacted 6 hours, and 200 DEG C of reactions obtained polybenzimidazole solution after 18 hours.After being cooled, this solution in impouring 3L water, obtains polymkeric substance precipitation, the NaHCO that is 3% by a large amount of mass concentrations by this polymkeric substance precipitation
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, collecting precipitation dry 58g polybenzimidazole resin (PBI-7, the m in counter structure formula 4: n=0.5: 0.5), the number-average molecular weight of this resin is 8.8 × 10 of obtaining
4.The physical and chemical performance of this resin is as shown in table 1.
Get gained polybenzimidazole 10g, add 100mL DMSO, be heated with stirring to and reflux 4 hours, obtain homogeneous polymer solution.Appropriate above-mentioned polymkeric substance preparation liquid curtain coating, on clean sheet glass or other carriers, is placed in to 60 DEG C of baking oven thermal treatments 8 hours, 80 DEG C 4 hours, 120 DEG C 5 hours, 180 DEG C 10 hours, be cooled to room temperature, after demoulding, obtain polybenzimidazole film, the performance of this film is as shown in table 2.
Above-mentioned film is soaked in mass concentration 65% phosphoric acid solution to 8 days, take out, rinse out surface acid solution with deionized water rapidly, and sop up surface-moisture with filter paper, obtain polybenzimidazole/phosphoric acid composite proton exchange membrane material, the performance of this material is as shown in table 2.
Embodiment 8,
Under nitrogen protection; prepared by 18.2g embodiment 32,5-two (2,3; 4; 6-tetrafluoro-5-carboxyl benzene) oxadiazole, 24.1g 5-(3,5-trifluoromethyl-phenoxy group)-m-phthalic acid and 23g 3; 3 '; 4,4 '-tetramine yl diphenyl ether (above-mentioned three's mol ratio is 0.4: 0.6: 1), adds in 680g polyphosphoric acid and is uniformly mixed.Said mixture is slowly heated to 60 DEG C of reactions 8 hours, and 120 DEG C are reacted 5 hours, and 210 DEG C of reactions obtained polybenzimidazole solution after 16 hours.After being cooled, this solution in impouring 16L water, obtains polymkeric substance precipitation, the Na that is 6% by a large amount of mass concentrations by this polymkeric substance precipitation
2cO
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, collecting precipitation dry polybenzimidazole resin (PBI-8, the m in counter structure formula 4: n=0.4: 0.6), the number-average molecular weight of this resin is 9.8 × 10 of obtaining
4.The physical and chemical performance of this resin is as shown in table 1.
Get gained polybenzimidazole 10g, add 120mL NMP, be heated with stirring to and reflux 5 hours, obtain homogeneous polymer solution.Appropriate above-mentioned polymkeric substance preparation liquid curtain coating, on clean sheet glass or other carriers, is placed in to 60 DEG C of baking oven thermal treatments 10 hours, 80 DEG C 4 hours, 120 DEG C 6 hours, 180 DEG C 16 hours, be cooled to room temperature, after demoulding, obtain polybenzimidazole film, the performance of this film is as shown in table 2.
Above-mentioned film is soaked in mass concentration 90% phosphoric acid solution to 5 days, take out, rinse out surface acid solution with deionized water rapidly, and sop up surface-moisture with filter paper, obtain polybenzimidazole/phosphoric acid composite proton exchange membrane material, the performance of this material is as shown in table 2.
The basic materialization performance of table 1, polybenzimidazole resin provided by the invention
asecond-order transition temperature adopts DMA test;
btensile strength, elongation at break is by GB GB1040 test
As shown in Table 1, polybenzimidazole resin provided by the invention can be dissolved in conventional organic solvent (as DMSO) under condition of normal pressure, and solubleness can reach 3-11%; And have good resistance toheat, its second-order transition temperature can reach 282-366 DEG C.
Table 2, for the correlated performance of the polybenzimidazole membrane of fuel cell
apBI film properties is tested referring to document [Feng SG et al., Journal of Membrane Science, 2009,335 (1-2): 13-20];
bthe probe temperature of PBI film is 30 DEG C;
cpBI/H
3pO
4the probe temperature of composite membrane is 180 DEG C, and the relative humidity of test environment is 5%.
As shown in Table 2, utilize polybenzimidazole resin provided by the invention to prepare the polybenzimidazole/phosphoric acid composite proton exchange membrane material of gained for fuel cell, antioxidant property excellence, can reach 3000-9000 hour work-ing life, thereby can be used as high temperature proton exchange film for fuel cell, there is important using value.
Claims (18)
1. general structure compound as shown in Equation 3:
In formula 3, Ar is
Substituent X 1, X2, X3, X4 are optionally all H or F, and wherein at least one is F.
2. the method for preparing compound shown in claim 1 Chinese style 3, comprises the steps:
1) under inert atmosphere protection, compound shown in formula 1, hydrazine hydrate and polyphosphoric acid mixing post-heating are made to reactants dissolved to 50-80 DEG C, and then be warming up to 120-200 DEG C and react, reaction finish after by reaction mixture impouring deionized water, filter collecting precipitation, gained is precipitated through soda lye wash, obtain compound shown in formula 2;
Wherein, the definition of the Ar in formula 1 and formula 2 is with the Ar in claim 1 Chinese style 3;
2) compound shown in formula 2 and oxygenant are carried out to oxidizing reaction, obtain the compound shown in described formula 3.
3. method according to claim 2, is characterized in that: step 1) in, the molfraction of the compound shown in formula 1, hydrazine hydrate and polyphosphoric acid is than being 2-2.2:1:5-20; Described inert atmosphere is nitrogen or argon gas atmosphere; The reaction times of described reaction is 8-24 hour;
Step 2) in, described oxygenant is potassium permanganate; Compound shown in described formula 2 is 1:3-10 with the molfraction ratio of described oxygenant; The reaction solvent of described oxidizing reaction is the mixed solvent of water and pyridine, and wherein, water and pyridine mass ratio are 1:(0.5-2.5); Described oxidizing reaction is carried out under reflux state, and the reaction times is 2-100 hour.
4. method according to claim 3, is characterized in that: step 1) in, the molfraction of the compound shown in formula 1, hydrazine hydrate and polyphosphoric acid is than being 2.1:1:15; Described inert atmosphere is nitrogen or argon gas atmosphere; The reaction times of described reaction is 15 hours;
Step 2) in, described oxygenant is potassium permanganate; Compound shown in described formula 2 is 1:4 with the molfraction ratio of described oxygenant; The reaction solvent of described oxidizing reaction is the mixed solvent of water and pyridine, and wherein, water and pyridine mass ratio are 1:1; Described oxidizing reaction is carried out under reflux state, and the reaction times is 20 hours.
5. general structure polybenzimidazole polymer as shown in Equation 4:
In formula 4, n:m=(1000-0): (0-1000), and m is not that 0, n equals or is not equal to 0;
In formula 4, the definition of Ar is with the Ar in formula 3 described in claim 1;
6. polymkeric substance according to claim 5, is characterized in that: in described formula 4, n is not equal to 0, n:m=(0.1-1) in described formula 4: (0.1-1).
7. polymkeric substance according to claim 6, is characterized in that: n:m=(0.3-0.9) in described formula 4: (0.3-0.9).
8. polymkeric substance according to claim 6, is characterized in that: n:m=(0.2-0.8) in described formula 4: (0.2-0.8).
9. according to the polymkeric substance described in any one in claim 5-8, it is characterized in that: the number-average molecular weight of the polymkeric substance shown in described formula 4 is 1 × 10
4-20 × 10
4;
Polymkeric substance shown in described formula 4 is random copolymers, segmented copolymer or the alternating copolymer of the composition of two portions repeated structural unit shown in described formula 4.
10. polymkeric substance according to claim 9, is characterized in that: the number-average molecular weight of the polymkeric substance shown in described formula 4 is 8 × 10
4-10 × 10
4.
11. prepare the method for polybenzimidazole polymer shown in claim 5 Chinese style 4, comprise the steps:
Under inert atmosphere protection, compound shown in formula 3 described in claim 1, compound diacid monomer, tetramine monomers and polyphosphoric acid are mixed, or compound shown in formula 3 described in claim 1, tetramine monomers and polyphosphoric acid are mixed; First react at 60-80 DEG C, then be warming up to 120-140 DEG C and react, be finally warming up to 160-250 DEG C and react, obtain the solution containing polybenzimidazole polymer shown in formula 4;
Wherein, described compound diacid monomer be selected from following any one: m-phthalic acid, terephthalic acid, 2,6 dicarboxyl pyridines, 3,5 dicarboxyl pyridines, 1, two (the 4-carboxyl)-phenoxy group-benzene, 1 of 4-, two (the 4-carboxyl)-phenoxy group-benzene, 1 of 3-, two (the 3-carboxyl)-phenoxy group-benzene, 1 of 3-, two (the 3-carboxyl)-phenoxy group-benzene of 4-, 5-(3,5-trifluoromethyl-phenoxy group)-m-phthalic acid, 1,2-bis trifluoromethyl-3, two ((4-carboxyl)-phenyl) methane and the 5-sodium sulfonate group-m-phthalic acids of 4-;
Described tetramine monomers be selected from following any one: 3,3 ', 4,4 '-tetramine yl diphenyl ether, 3,3 ', 4,4 '-tetramine base biphenyl, 1,2,4,5-tetramine base benzene, 3,3 ', 4,4 '-tetra-aminobenzophenones, 3,3 ', 4,4 '-tetramine base sulfobenzide and 1,2-dimethyl-3, two (4-(3,4-, the bis-amido benzene oxygen)-benzene) methylmethanes of 4-.
12. methods according to claim 11, is characterized in that: shown in described formula 3, the mol ratio of compound, compound diacid monomer, tetramine monomers is x:(1-x): 1, wherein x=0-1 but do not comprise 0;
Shown in described formula 3, compound, compound diacid monomer, the total mass of tetramine monomers and the ratio of quality and the number of copies of polyphosphoric acid are 100:300-4000;
Described is 2-8 hour 60-80 DEG C of time of reacting, and described is 4-6 hour 120-140 DEG C of time of reacting, and 160-250 DEG C of time of reacting is 12-24 hour.
13. according to the method described in claim 11 or 12, it is characterized in that: described method also comprises the steps: the described solution containing polybenzimidazole polymer shown in formula 4 to cool and be placed in water, obtain polymkeric substance precipitation, the NaHCO that is 1-10% by mass concentration by described polymkeric substance precipitation
3or Na
2cO
3the aqueous solution fully washs neutralization, then is washed till neutrality with deionized water, and collecting precipitation is also dry, obtains fluorine-containing polybenzimidazole polymer.
The application of polybenzimidazole polymer in 14. claim 5-10 described in any one in following any one product of preparation: polybenzimidazole film, polybenzimidazole/phosphoric acid compound proton exchange membrane, separatory membrane, sensor, high-temperature fibre, high temperature resistant composite and binding agent.
15. 1 kinds of polybenzimidazole films, prepare by the following method: polybenzimidazole polymer and organic solvent described in any one in claim 5-10 are mixed, carry out back flow reaction, obtain the preparation liquid of polybenzimidazole polymer; Described preparation liquid is coated on carrier and heat-treated masking, and masking finishes rear cooling demoulding, obtains described polybenzimidazole film.
16. polybenzimidazole films according to claim 15, it is characterized in that: described organic solvent be selected from following at least one: N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide, meta-cresol, p-cresol, dimethyl sulfoxide (DMSO), gamma-butyrolactone, sulfobenzide and tetramethylene sulfone;
The ratio of quality and the number of copies of described polybenzimidazole polymer and described organic solvent is 10:100-200;
The step of described thermal treatment masking comprises successively: at 60 DEG C of thermal treatment 6-16 hours, 80 DEG C thermal treatment 2-8 hour, 120 DEG C thermal treatment 1-6 hour and 180 DEG C of thermal treatment 10-16 hour.
17. 1 kinds of polybenzimidazole/phosphoric acid compound proton exchange membranes, prepare by the following method: the polybenzimidazole film described in claim 15 or 16 is soaked in phosphate aqueous solution, after taking-up, clean with deionized water, obtain described polybenzimidazole/phosphoric acid compound proton exchange membrane;
Wherein, in described phosphate aqueous solution, the mass concentration of phosphoric acid is 50-90%, and the time of described immersion is 5-10 days.
Polybenzimidazole/phosphoric acid compound proton exchange membrane described in 18. claims 17 is in the application of preparing in Proton Exchange Membrane Fuel Cells.
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