CN101709029A - Polybenzimidazole material and midbody organic diacid thereof as well as preparation methods thereof - Google Patents
Polybenzimidazole material and midbody organic diacid thereof as well as preparation methods thereof Download PDFInfo
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Abstract
The invention discloses a polybenzimidazole material and midbody organic diacid thereof as well as preparation methods thereof. The preparation methods comprise the following steps of: condensing fluorine-containing halide and 3,5-dimethyl phenol under the action of basic catalyst to generate fluorine-containing side-chain-substituted m-dimethyl benzene derivatives then oxidizing the obtained fluorine-containing side-substituted m-dimethyl benzene derivatives by potassium permanganate or nitric acid to obtain side-chain fluorine-containing organic diacid monomer and derivatives thereof; and carrying out polycondensation on the side-chain fluorine-containing organic diacid monomer, compound diacid monomer and tetramine monomer in polyphosphoric acid to generate the side-chain fluorine-containing soluble polybenzimidazole material . The prepared polybenzimidazole material has favorable heat resistance performance and solubility performance and can be used as high-temperature proton exchange membranes, separation membranes, sensors, heat resistance materials, composite materials, caking agents and other functional materials for fuel cells.
Description
Technical field
The invention belongs to the functional high molecule material preparing technical field, relate to polybenzimidazole material and intermediate organic diacid thereof and their preparation method.
Background technology
Polybenzimidazole material is as a kind of high performance engineering plastics, have excellent heat-resistant stability can and the mechanics mechanical property, acid and alkali-resistance, radiation hardness, can be widely used in industries such as Aeronautics and Astronautics, electric power, electronics, machinery.But because the molecule chain rigidity is too strong, can only be dissolved in the organic solvent of seldom counting and strong acid, because the machine-shaping difficulty has limited its range of application, therefore, improve the dissolving processing characteristics of polybenzimidazole, be the key that this class material obtains broader applications.
Along with the development of fuel cell technology in recent years, the application of polybenzimidazole material in Proton Exchange Membrane Fuel Cells (PEMFC) is subjected to people's attention gradually.The core material of proton exchange membrane PEMFC plays the effect of transmission proton, obstruct fuel and air therein.Unique commercial proton exchange membrane is a perfluoro sulfonic acid membrane at present, it has high proton conductivity, excellent in chemical is stable, shortcoming is the cost height, use temperature low (below 100 ℃), lower temperature operation condition faces such as Catalyst for CO fuel cell to poison when 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 total energy are imitated low inferior practical problems, and to improve the operating temperature of PEMFC, must development of new high-temperature resistant proton exchange membrane material.Polybenzimidazole is because the second-order transition temperature height, after mixing with mineral acid such as phosphoric acid, can realize than the proton conduction under anhydrous condition and the comparatively high temps, is considered to the 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 because the H that generates in the PEMFC cathode electrode reaction process
2O
2And-OH or/and-molecular chain of OOH free radical in can degraded films, make film forming oxidative degradation.Because the polybenzimidazole main chain is carbon-carbon bond and hydrocarbon key, its resistance to oxidation stability is compared with perfluoro sulfonic acid membrane and is still waiting further raising.
In sum, although polybenzimidazole material has a series of excellent properties,, must improve its dissolving processing characteristics and resistance to oxidation stability if can in PEMFC, obtain to use.
Summary of the invention
The purpose of this invention is to provide a kind of polybenzimidazole material and intermediate organic diacid thereof and their preparation method.
The organic diacid compound that side chain provided by the invention is fluorine-containing, its general structure be suc as formula shown in the I,
(formula I)
In the described formula I general structure,
The method of the organic diacid compound that the above-mentioned side chain of preparation provided by the invention is fluorine-containing comprises the steps:
1) under inert atmosphere protection, with structural formula is the fluorine-containing halogenated organic compound, 3 shown in the R-X, 5-xylenol, catalyzer and dewatering agent toluene carry out back flow reaction in organic solvent, be warming up to 120-170 ℃ of continuation reaction after getting rid of toluene, obtain compound shown in the formula II, be the resorcinol derivatives of fluorine-containing side substitution;
(formula II)
2) compound shown in the described formula II is carried out oxidizing reaction with oxygenant in solvent, obtain the fluorine-containing organic diacid compound of described side chain.
The preparation flow of this method is as follows:
In the step 1) of this method, among described formula R-X,
X is Cl, Br or I;
Described catalyzer is selected from KF, KOH, NaOH, Na
2CO
3And K
2CO
3In at least a; Described organic solvent is selected from least a in ether, chloroform, methylene dichloride, sherwood oil, hexane, tetrahydrofuran (THF), benzene and the toluene; Described structural formula is the fluorine-containing halogenated organic compound, 3 shown in the R-X, the ratio of quality and the number of copies of 5-xylenol, catalyzer, toluene and described organic solvent is 110-400: 100-150: 15-80: 50-150: 600-2000, specifically can be 150-350: 105-145: 16-75: 55-145: 650-1950,150-300: 110-140: 20-70: 60-140: 700-1900 or 200-300: 120-140: 25-65: 65-135: 750-1850, preferred 150: 100: 30: 80: 800; Described inert atmosphere is nitrogen or argon gas atmosphere;
The reaction times of back flow reaction is 2-8 hour, preferred 6 hours; The described 120-170 of being warming up to ℃ of reaction times of continuing reaction is 4-24 hour, preferred 16 hours;
After the described 120-170 of being warming up to ℃ of continuation reaction finishes, reaction system is done following processing:
It is 0.5-1 with the volume ratio that reaction system is placed the second alcohol and water: 0.2-1 blended mixed solution, filtration extract with water-insoluble organic solvent after collecting filtrate, and after the collection oil phase was also concentrated, vacuum distilling obtained compound shown in the formula II; Described water-insoluble organic solvent is selected from least a in ether, chloroform, methylene dichloride, sherwood oil, hexane, tetrahydrofuran (THF), benzene and the toluene.
Described step 2) in, the used oxygenant of oxidizing reaction is potassium permanganate or nitric acid; The ratio of quality and the number of copies of compound shown in the described formula II, described solvent and described oxygenant is 100-200: 300-800: 20-200, specifically can be 110-190: 310-790: 25-190,120-180: 320-750: 30-180,150-190: 350-700: 35-180, preferred 150: 500: 50; The temperature of reaction of oxidizing reaction is the boiling point of described solvent, and the reaction times of oxidizing reaction is 2-48 hour, preferred 10 hours.
Polybenzimidazole polymer provided by the invention, its general structure shown in formula III,
Shown in the formula III, n: m=(1000-0): (0-1000), and m does not comprise 0; N equals or is not equal to 0.When n ≠ 0, n: m specifically can be 0.2: 0.8,0.4: 0.6,0.3: 0.7,0.7: 0.3,0.5: 0.5,0.6: 0.4,0.1-1: 0.1-1,0.3-0.9: 0.3-0.9 or 0.2-0.8: 0.2-0.8;
Above-mentioned polybenzimidazole polymer can be random copolymers, segmented copolymer or the alternating copolymer of being made up of two portions repeated structural unit shown in the formula III general structure.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, preferred 8 * 10
4-10 * 10
4
The method of the above-mentioned polybenzimidazole polymer of preparation provided by the invention; comprise the steps: under inert atmosphere protection; the organic diacid compound that described side chain is fluorine-containing, compound diacid monomer, tetramine monomers and polyphosphoric acid (PPA) mixing; react at 60-80 ℃ earlier; being warming up to 120-140 ℃ again reacts; be warming up at last 160-250 ℃ react after, obtain described polybenzimidazole polymer.
The preparation flow of this method is as follows:
In this method, described compound diacid monomer is used for telomerized polymer segment rigidity and solubility property, be selected from 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, 1 of 4-, 2-bis trifluoromethyl-3, at least a in two ((the 4-carboxyl)-phenyl) methane of 4-and the 5-sodium sulfonate group-Jian 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 '-tetramine base sulfobenzide and 3,3 ', 4,4 '-tetramine base benzophenone, 1,2-dimethyl-3, two (4-(3, the 4-two amido benzene oxygen)-benzene) methylmethanes of 4-, at least a.
The mol ratio of the fluorine-containing organic diacid compound of described side chain, compound diacid monomer, tetramine monomers is x: (1-x): 1, and x=0-1 but do not comprise 0 wherein; The total amount of organic diacid compound, compound diacid monomer and 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 ℃ of time of reacting is 4-6 hour, and 120-140 ℃ of time of reacting is 4-6 hour, and 160-250 ℃ of time of reacting is 12-24 hour.
After reaction finishes, can do following processing to reaction system: polybenzimidazole solution is cooled to be placed in the big water gaging, obtains polymer precipitation, is the NaHCO of 1-10% with a large amount of mass percentage concentration with this polymer precipitation
3Or Na
2CO
3The neutralization of aqueous solution thorough washing is washed till neutrality with deionized water again, and collecting precipitation is also dry, obtains polybenzimidazole resin.
The application of above-mentioned polybenzimidazole polymer in preparation polybenzimidazole film, polybenzimidazole/phosphoric acid composite proton exchange membrane material, separatory membrane, transmitter, high-temperature fibre, high temperature resistant composite and binding agent also belongs to protection scope of the present invention.
Wherein, the described method for preparing the polybenzimidazole film, can carry out according to the ordinary method that comprises the steps: with described polybenzimidazole polymer and organic solvent mixing, obtain the preparation liquid of polybenzimidazole polymer after the back flow reaction, described preparation liquid is coated carrier place baking oven thermal treatment system film, cooling and demolding obtains described polybenzimidazole film; Described organic solvent is selected from N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, at least a in N '-dimethyl formamide, meta-cresol, p-cresol, dimethyl sulfoxide (DMSO), gamma-butyrolactone, sulfobenzide and the tetramethylene sulfone; The ratio of quality and the number of copies of described polybenzimidazole polymer and organic solvent is 10: 100-200; Described heat treatment step comprised successively: 60 ℃ of thermal treatment 6-16 hours, 80 ℃ thermal treatment 2-6 hour, 120 ℃ thermal treatment 1-6 hour and 180 ℃ thermal treatment 2-12 hour.
The described method for preparing polybenzimidazole/phosphoric acid composite proton exchange membrane material, can carry out according to the ordinary method that comprises the steps:
1) with described polybenzimidazole polymer and organic solvent mixing, obtain the preparation liquid of polybenzimidazole polymer after the back flow reaction, described preparation liquid to be coated carrier place baking oven through thermal treatment system film, cooling and demolding obtains described polybenzimidazole film;
2) described polybenzimidazole film is soaked in the phosphate aqueous solution, cleans with deionized water rapidly after the taking-up, obtain described polybenzimidazole/phosphoric acid composite proton exchange membrane material.
Described organic solvent is selected from N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, at least a in N '-dimethyl formamide, meta-cresol, p-cresol, dimethyl sulfoxide (DMSO), gamma-butyrolactone, sulfobenzide and the tetramethylene sulfone; Described heat treatment step comprised successively: 60 ℃ of thermal treatment 6-16 hours, 80 ℃ thermal treatment 2-6 hour, 120 ℃ thermal treatment 1-6 hour and 180 ℃ thermal treatment 2-10 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 50-80%, and the time of described soaking step is 6-10 days.
The present invention has significantly improved the polybenzimidazole solubility property by introducing big side group to reduce the tightly packed of macromolecular chain in polymer molecule; Simultaneously, in polymkeric substance, introduce fluoro-containing group, given more excellent oxidation-resistance energy of polybenzimidazole.The method of the organic diacid that preparation side chain provided by the invention is fluorine-containing has the advantages that raw material is easy to get, synthetic route succinct, be suitable for scale operation.Polybenzimidazole resin provided by the present invention can be dissolved under condition of normal pressure in the organic solvent commonly used, solubleness can reach 5-10%, has good heat-resistant, and its second-order transition temperature reaches 290-380 ℃, antioxidant property excellence in fuel cell, can reach 3000-8000 hour work-ing life.Can be used as high temperature proton exchange film for fuel cell, transmitter, high-temperature fibre, matrix material, binding agent and other functional materialss, have important use and be worth.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1,
At N
2Protection adds 175 parts of p-Fluoro bromo benzenes, 3,122 parts of 5-xylenols down in there-necked flask; 80 parts of Na2CO3,200 parts of 800 parts of dimethyl formamides and toluene are opened and are stirred; slowly be heated to back flow reaction 5h; get rid of toluene, be warming up to 130 ℃ of reaction 10h, reaction mixture is inclined in the ethanol/water solution; use extracted with diethyl ether 3 times after filtering collection filtrate; after the collection oil phase also concentrated, vacuum distilling obtained 3,5-dimethyl-(4-fluoro-phenoxy group)-benzene.In the 2L there-necked flask, add 5-(4-fluoro-phenoxy group)-1,100 parts of 3-dimethyl benzenes, 500 parts in water, 500 parts of pyridines are heated to backflow, and slowly gradation adds potassium permanganate and adds 100 parts, back flow reaction 7 days, in excessive 10% hydrochloric acid of reactant impouring, filter collecting precipitation, throw out is obtained 5-(4-fluoro-phenoxy group)-m-phthalic acid after with ethyl alcohol recrystallization and vacuum-drying.Under nitrogen or argon shield, with 5-(4-fluoro-the phenoxy group)-m-phthalic acid of 10 parts of weight, 9.7 parts of 5-sodium sulfonate-m-phthalic acids, 16 part 3,3 ', 4,4 '-tetramine yl diphenyl ether adds in 350 parts of polyphosphoric acid and mixes.Said mixture slowly is heated to 60 ℃ of reactions 4 hours, 120 ℃ were reacted 4 hours, and 160 ℃ of reactions obtained polybenzimidazole solution after 12 hours, in cold back impouring 2 premium on currency that go to lower the temperature of this solution, obtaining polymer precipitation, is the NaHCO of 1wt% with a large amount of concentration with this polymkeric substance
3Aqueous solution thorough washing neutralization is washed till neutrality with deionized water again, and collecting precipitation and drying obtain polybenzimidazole resin (PBI-1, m in the counter structure formula III: n=1: 1), the number-average molecular weight of this resin is 8.5 * 10
4The physical and chemical performance of this resin is as shown in table 1.
Get 10 parts of gained polybenzimidazole, add 200 parts of dimethyl sulfoxide (DMSO), be heated with stirring to and refluxed 3 hours, obtain homogeneous polymer solution.An amount of above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, was placed 60 ℃ of baking oven thermal treatments 6 hours, 80 ℃ 2 hours, 120 ℃ 2 hours, 180 ℃ 12 hours, be cooled to room temperature, obtain the polybenzimidazole film behind the demoulding, the performance of this film is as shown in table 2.
Embodiment 2,
At N
2Protection adds 225 parts of 4-methyl bromobenzene trifluorides, 3,122 parts of 5-xylenols down in there-necked flask; 80 parts of K2CO3,300 parts of 1000 parts of N,N-DIMETHYLACETAMIDEs and toluene are opened and are stirred; slowly be heated to back flow reaction 6h; get rid of toluene, be warming up to 140 ℃ of reaction 10h, reaction mixture is inclined in the ethanol/water solution; use extracted with diethyl ether 3 times after filtering collection filtrate; after the collection oil phase also concentrated, vacuum distilling obtained 3,5-dimethyl-(4-trifluoromethyl-phenoxy group)-benzene.Add 3 at the 1L of liner tetrafluoroethylene autoclave, 100 parts of 5-dimethyl-(4-trifluoromethyl-phenoxy group)-benzene, 500 parts in 50% nitric acid, at 150 ℃, 5atm reacted 3 hours down, after the cooling decompression, take out reaction mixture and filter collecting precipitation, throw out is obtained 5-(4-trifluoromethyl-phenoxy group)-m-phthalic acid after with ethanol/water recrystallization and vacuum-drying.Under nitrogen or argon shield, with 5-(4-trifluoromethyl-phenoxy group)-m-phthalic acid of 26 parts of weight, 3.3 parts of m-phthalic acids, 13.8 part 1,2,4,5-tetramine base benzene adds in 600 parts of polyphosphoric acid and mixes.Said mixture slowly is heated to 60 ℃ of reactions 4 hours, 120 ℃ were reacted 6 hours, and 200 ℃ of reactions obtained polybenzimidazole solution after 16 hours, in cold back impouring 3 premium on currency that go to lower the temperature of this solution, obtaining polymer precipitation, is the NaHCO of 5wt% with a large amount of concentration with this polymkeric substance
3Aqueous solution thorough washing neutralization is washed till neutrality with deionized water again, and collecting precipitation and drying obtain polybenzimidazole resin (PBI-2, m in the counter structure formula III: n=0.8: 0.2), the number-average molecular weight of this resin is 10 * 10
4The physical and chemical performance of this resin is as shown in table 1.
Get 10 parts of gained polybenzimidazole, add 200 parts of organic solvents, be heated with stirring to and refluxed 3 hours, obtain homogeneous polymer solution.An amount of above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, was placed 60 ℃ of baking oven thermal treatments 6 hours, 80 ℃ 4 hours, 120 ℃ 4 hours, 180 ℃ 10 hours, be cooled to room temperature, obtain the polybenzimidazole film behind the demoulding, the performance of this film is as shown in table 2.
Embodiment 3,
Under argon shield, in there-necked flask, add 3,250 parts of 5-trifluoromethyl chlorobenzenes, 3; 122 parts of 5-xylenols, 100 parts of KOH, 300 parts of 1000 parts of dimethyl sulfoxide (DMSO) and toluene; open and stir, slowly be heated to back flow reaction 5h, get rid of toluene; be warming up to 130 ℃ of reaction 12h, reaction mixture is inclined in the ethanol/water solution, filter and collect after the filtrate with chloroform extraction 3 times; after the collection oil phase also concentrates; vacuum distilling obtains 3,5-dimethyl-(3,5-trifluoromethyl-phenoxy group)-benzene.In the 2L there-necked flask, add 5-(4-fluoro-phenoxy group)-1,150 parts of 3-dimethyl benzenes, 600 parts in water, 600 parts of pyridines are heated to backflow, slowly gradation adds potassium permanganate and adds 120 parts, back flow reaction 6 days in excessive 10% hydrochloric acid of reactant impouring, is filtered collecting precipitation, throw out is obtained 5-(3,5-trifluoromethyl-phenoxy group)-m-phthalic acid after with ethanol/water recrystallization and vacuum-drying.Under nitrogen or argon shield, with 5-(3,5-trifluoromethyl-phenoxy group)-m-phthalic acid of 19.7 parts of weight, 12.8 part 3,3 ', 4,4 '-tetramine base ditane adds in 300 parts of polyphosphoric acid and mixes.Said mixture slowly is heated to 80 ℃ of reactions 2 hours, 130 ℃ were reacted 4 hours, and 210 ℃ of reactions obtained polybenzimidazole solution after 20 hours, in the cold a large amount of water of back impouring that go to lower the temperature of this solution, obtaining polymer precipitation, is the Na of 1wt% with a large amount of concentration with this polymkeric substance
2CO
3The neutralization of aqueous solution thorough washing is washed till neutrality with deionized water again, and collecting precipitation and drying obtain polybenzimidazole resin (PBI-3, n=0 in the counter structure formula III), and the number-average molecular weight of this resin is 9.2 * 10
4The physical and chemical performance of this resin is as shown in table 1.
Get 10 parts of gained polybenzimidazole, add 120 parts of organic solvents, be heated with stirring to and refluxed 6 hours, obtain homogeneous polymer solution.An amount of above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, was placed 60 ℃ of baking oven thermal treatments 6 hours, 80 ℃ 4 hours, 120 ℃ 4 hours, 180 ℃ 10 hours, be cooled to room temperature, obtain the polybenzimidazole film behind the demoulding, the performance of this film is as shown in table 2.Above-mentioned film was soaked in 50% phosphoric acid solution 10 days, takes 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 4,
Under nitrogen protection, with 5-(3-fluoro-the phenoxy group)-m-phthalic acid of 16.6 parts of weight, 6.8 part of 2,6 dicarboxyl pyridine and 27.7 part 3,3 ', 4,4 '-tetramine base sulfobenzide adds in 800 parts of polyphosphoric acid and mixes.Said mixture slowly is heated to 60 ℃ of reactions 4 hours, 120 ℃ were reacted 5 hours, and 210 ℃ of reactions obtained polybenzimidazole solution after 18 hours, in cold back impouring 6 premium on currency that go to lower the temperature of this solution, obtaining polymer precipitation, is the Na of 10wt% with a large amount of concentration with this polymkeric substance
HCO
3Aqueous solution thorough washing neutralization is washed till neutrality with deionized water again, and collecting precipitation and drying obtain polybenzimidazole resin (PBI-4, m in the counter structure formula III: n=0.6: 0.4), the number-average molecular weight of this resin is 8 * 10
4The physical and chemical performance of this resin is as shown in table 1.
Get 10 parts of gained polybenzimidazole, add 180 parts of organic solvents, be heated with stirring to and refluxed 6 hours, obtain homogeneous polymer solution.An amount of above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, was placed 60 ℃ of baking oven thermal treatments 6 hours, 80 ℃ 4 hours, 120 ℃ 4 hours, 180 ℃ 10 hours, be cooled to room temperature, obtain the polybenzimidazole film behind the demoulding, the performance of this film is as shown in table 2.Above-mentioned film was soaked in 70% phosphoric acid solution 8 days, takes 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 5,
Under argon shield, with 5-(4-trifluoromethyl-phenoxy group)-m-phthalic acid of 22.8 parts of weight, 10.5 part 1, two (the 3-carboxyl)-phenoxy group-benzene of 3-and 23 part 3,3 ', 4,4 '-tetramine yl diphenyl ether adds in 600 parts of polyphosphoric acid and mixes.Said mixture slowly is heated to 70 ℃ of reactions 5 hours, 140 ℃ were reacted 4 hours, and 200 ℃ of reactions obtained polybenzimidazole solution after 12 hours, in cold back impouring 4 premium on currency that go to lower the temperature of this solution, obtaining polymer precipitation, is the Na of 5wt% with a large amount of concentration with this polymkeric substance
2CO
3Aqueous solution thorough washing neutralization is washed till neutrality with deionized water again, and collecting precipitation and drying obtain polybenzimidazole resin (PBI-5, m in the counter structure formula III: n=0.7: 0.3), the number-average molecular weight of this resin is 8.7 * 10
4The physical and chemical performance of this resin is as shown in table 1.
Get 10 parts of gained polybenzimidazole, add 160 parts of organic solvents, be heated with stirring to and refluxed 3 hours, obtain homogeneous polymer solution.An amount of above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, was placed 60 ℃ of baking oven thermal treatments 10 hours, 80 ℃ 6 hours, 120 ℃ 6 hours, 180 ℃ 12 hours, be cooled to room temperature, obtain the polybenzimidazole film behind the demoulding, the performance of this film is as shown in table 2.Above-mentioned film was soaked in 80% phosphoric acid solution 10 days, takes 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; 5-(4-trifluoromethyl-phenoxy group)-m-phthalic acid with 9.7 parts of weight; 24.5 part 1; two (the 3-carboxyl)-phenoxy group-benzene of 4-and 44.1 part 1; 2-dimethyl-3; two (4-(3, the 4-two amido benzene oxygen)-benzene) methylmethanes of 4-add in 1200 parts of polyphosphoric acid and mix.Said mixture slowly is heated to 80 ℃ of reactions 6 hours, 140 ℃ were reacted 6 hours, and 250 ℃ of reactions obtained polybenzimidazole solution after 24 hours, in cold back impouring 10 premium on currency that go to lower the temperature of this solution, obtaining polymer precipitation, is the Na of 10wt% with a large amount of concentration with this polymkeric substance
2CO
3Aqueous solution thorough washing neutralization is washed till neutrality with deionized water again, and collecting precipitation and drying obtain polybenzimidazole resin (PBI-6, m in the counter structure formula III: n=0.3: 0.7), the number-average molecular weight of this resin is 9.6 * 10
4The physical and chemical performance of this resin is as shown in table 1.
Get 15 parts of gained polybenzimidazole, add 160 parts of organic solvents, be heated with stirring to and refluxed 3 hours, obtain homogeneous polymer solution.An amount of above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, was placed 60 ℃ of baking oven thermal treatments 16 hours, 80 ℃ 6 hours, 120 ℃ 6 hours, 180 ℃ 12 hours, be cooled to room temperature, obtain the polybenzimidazole film behind the demoulding, the performance of this film is as shown in table 2.Above-mentioned film was soaked in 80% phosphoric acid solution 6 days, takes 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, with 5-(3,5-trifluoromethyl-phenoxy group)-m-phthalic acid of 20 parts of weight, 13.5 parts of 5-sodium sulfonate group-Jian phthalic acids and 27.7 part 3,3 ', 4,4 '-tetramine base sulfobenzide adds in 500 parts of polyphosphoric acid and mixes.Said mixture slowly is heated to 80 ℃ of reactions 4 hours, 140 ℃ were reacted 5 hours, and 200 ℃ of reactions obtained polybenzimidazole solution after 15 hours, in cold back impouring 3 premium on currency that go to lower the temperature of this solution, obtaining polymer precipitation, is the NaHCO of 3wt% with a large amount of concentration with this polymkeric substance
3Aqueous solution thorough washing neutralization is washed till neutrality with deionized water again, and collecting precipitation and drying obtain polybenzimidazole resin (PBI-7, m in the counter structure formula III: n=0.5: 0.5), the number-average molecular weight of this resin is 8.9 * 10
4The physical and chemical performance of this resin is as shown in table 1.
Get 10 parts of gained polybenzimidazole, add 150 parts of organic solvents, be heated with stirring to and refluxed 4 hours, obtain homogeneous polymer solution.An amount of above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, was placed 60 ℃ of baking oven thermal treatments 8 hours, 80 ℃ 4 hours, 120 ℃ 5 hours, 180 ℃ 10 hours, be cooled to room temperature, obtain the polybenzimidazole film behind the demoulding, the performance of this film is as shown in table 2.Above-mentioned film was soaked in 70% phosphoric acid solution 8 days, takes 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, with 5-(3,5-trifluoromethyl-phenoxy group)-m-phthalic acid of 15.7 parts of weight, 23.5 part 1; 2-bis trifluoromethyl-3, two ((the 4-carboxyl)-phenyl) methane of 4-and 46 part 3,3 '; 4,4 '-tetramine yl diphenyl ether adds in 800 parts of polyphosphoric acid and mixes.Said mixture slowly is heated to 70 ℃ of reactions 4 hours, 120 ℃ were reacted 6 hours, and 220 ℃ of reactions obtained polybenzimidazole solution after 12 hours, in cold back impouring 12 premium on currency that go to lower the temperature of this solution, obtaining polymer precipitation, is the Na2CO of 6wt% with a large amount of concentration with this polymkeric substance
3Aqueous solution thorough washing neutralization is washed till neutrality with deionized water again, and collecting precipitation and drying obtain polybenzimidazole resin (PBI-8, m in the counter structure formula III: n=0.4: 0.6), the number-average molecular weight of this resin is 9.5 * 10
4The physical and chemical performance of this resin is as shown in table 1.
Get 10 parts of gained polybenzimidazole, add 100 parts of organic solvents, be heated with stirring to and refluxed 4 hours, obtain homogeneous polymer solution.An amount of above-mentioned polymkeric substance preparation liquid curtain coating on clean sheet glass or other carriers, was placed 60 ℃ of baking oven thermal treatments 6 hours, 80 ℃ 2 hours, 120 ℃ 4 hours, 180 ℃ 10 hours, be cooled to room temperature, obtain the polybenzimidazole film behind the demoulding, the performance of this film is as shown in table 2.Above-mentioned film was soaked in 80% phosphoric acid solution 6 days, takes 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
As shown in Table 1, polybenzimidazole resin provided by the invention can be dissolved under condition of normal pressure in the organic solvent commonly used (as DMSO), and solubleness can reach 5-10%, has good heat-resistant, and its second-order transition temperature can reach 290-380 ℃.
Table 2, be used for the correlated performance of the polybenzimidazole membrane of fuel cell
| Water-intake rate a??(wt％) | Swelling capacity a??(％) | Methanol permeability a??cm 2s -1 | Electric conductivity b??Scm -1 | Life-span b??hour | |
| ??PBI-1 | ??28 | ??＜1 | ??1.4×10 -8 | ??4.3×10 -2 | ??3200 |
| ??PBI-2 | ??20 | ??＜1 | ??1.7×10 -8 | ??5.7×10 -2 | ??4500 |
| ??PBI-3 | ??22 | ??＜1 | ??2.3×10 -8 | ??6.4×10 -2 | ??4300 |
| ??PBI-4 | ??24 | ??＜1 | ??1.3×10 -8 | ??8.6×10 -2 | ??4800 |
| ??PBI-5 | ??26 | ??＜1 | ??2.6×10 -8 | ??4.3×10 -2 | ??6200 |
| ??PBI-6 | ??26 | ??＜1 | ??2.5×10 -8 | ??6.5×10 -2 | ??7600 |
| ??PBI-7 | ??35 | ??＜1 | ??6.02×10 -8 | ??1.1×10 -1 | ??5700 |
| ??PBI-8 | ??25 | ??＜1 | ??1.1×10 -8 | ??9.4×10 -2 | ??8100 |
aThe probe temperature of PBI film is 30 ℃.
bPBI/H
3PO
4The probe temperature of composite membrane is 180 ℃, and the relative humidity of test environment is 5%.
As shown in Table 2, polybenzimidazole/phosphoric acid the composite proton exchange membrane material that utilizes polybenzimidazole resin provided by the invention to prepare gained to be used for fuel cell, the antioxidant property excellence, can reach 3000-8000 hour work-ing life, thereby can be used as high temperature proton exchange film for fuel cell, have important use and be worth.
Claims (10)
1. the fluorine-containing organic diacid compound of side chain shown in the formula I,
(formula I)
In the described formula I general structure,
2. a method for preparing the fluorine-containing organic diacid compound of the described side chain of claim 1 comprises the steps:
1) under inert atmosphere protection, with structural formula is the fluorine-containing halogenated organic compound, 3 shown in the R-X, 5-xylenol, catalyzer and toluene carry out back flow reaction in organic solvent, be warming up to 120-170 ℃ behind the eliminating toluene and continue reaction, obtain compound shown in the formula II;
(formula II)
2) compound shown in the described formula II is carried out oxidizing reaction with oxygenant in solvent, obtain the fluorine-containing organic diacid compound of described side chain.
3. method according to claim 2 is characterized in that: in the described step 1), and among described formula R-X,
X is Cl, Br or I;
Described catalyzer is selected from KF, KOH, NaOH, Na
2CO
3And K
2CO
3In at least a; Described organic solvent is selected from least a in ether, chloroform, methylene dichloride, sherwood oil, hexane, tetrahydrofuran (THF), benzene and the toluene;
Described step 2) in, the used oxygenant of oxidizing reaction is potassium permanganate or nitric acid.
4. according to claim 2 or 3 described methods, it is characterized in that: in the described step 1), described structural formula is the fluorine-containing halogenated organic compound, 3 shown in the R-X, the ratio of quality and the number of copies of 5-xylenol, catalyzer, toluene and described organic solvent is 110-400: 100-150: 15-80: 50-150: 600-2000, preferred 150: 100: 30: 80: 800; Described inert atmosphere is nitrogen or argon gas atmosphere;
The reaction times of back flow reaction is 2-8 hour, preferred 6 hours; The described 120-170 of being warming up to ℃ of reaction times of continuing reaction is 4-24 hour, preferred 16 hours;
Described step 2) in, the ratio of quality and the number of copies of compound shown in the described formula II, described solvent and described oxygenant is 100-200: 300-800: 20-200, preferred 150: 500: 50;
The temperature of reaction of oxidizing reaction is the boiling point of described solvent, and the reaction times of oxidizing reaction is 2-48 hour, preferred 10 hours.
5. according to the arbitrary described method of claim 2-4, it is characterized in that: in the described step 1), after the described 120-170 of being warming up to ℃ of continuation reaction finishes, reaction system is done following processing:
It is 0.5-1 with the volume ratio that reaction system is placed the second alcohol and water: 0.2-1 blended mixed solution, filtration extract with water-insoluble organic solvent after collecting filtrate, and after the collection oil phase was also concentrated, vacuum distilling obtained compound shown in the formula II; Described water-insoluble organic solvent is selected from least a in ether, chloroform, methylene dichloride, sherwood oil, hexane, tetrahydrofuran (THF), benzene and the toluene.
6. polybenzimidazole polymer shown in the general formula III,
(formula III)
In the described formula III, n: m=(1000-0): (0-1000), and m does not comprise 0;
The number-average molecular weight of described polybenzimidazole polymer is 1 * 10
4-20 * 10
4
7. polymkeric substance according to claim 6 is characterized in that: in the described formula III, and n: m=0.2-0.9: 0.2-0.9; The number-average molecular weight of described polybenzimidazole polymer is 8 * 10
4-10 * 10
4
8. method for preparing claim 6 or 7 described polybenzimidazole polymers, comprise the steps: under inert atmosphere protection, the organic diacid compound that the described side chain of claim 1 is fluorine-containing, compound diacid monomer, tetramine monomers and polyphosphoric acid mixing, react at 60-80 ℃ earlier, being warming up to 120-140 ℃ again reacts, be warming up at last 160-250 ℃ react after, obtain described polybenzimidazole polymer;
Described compound diacid monomer is selected from 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, 1 of 4-, 2-bis trifluoromethyl-3, at least a in two ((the 4-carboxyl)-phenyl) methane of 4-and the 5-sodium sulfonate group-abridged edition dioctyl phthalate;
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 '-tetramine base sulfobenzide and 3,3 ', 4,4 '-tetramine base benzophenone and 1,2-dimethyl-3, at least a in two (4-(3, the 4-two amido benzene oxygen)-benzene) methylmethanes of 4-.
9. method according to claim 8 is characterized in that: the mol ratio of the fluorine-containing organic diacid compound of the described side chain of claim 1, described compound diacid monomer, described tetramine monomers is x: (1-x): 1, wherein, x=0-1 but do not comprise 0; The total amount of organic diacid compound, described compound diacid monomer and described tetramine monomers that described side chain is fluorine-containing and the ratio of quality and the number of copies of described polyphosphoric acid are 100: 300-4000;
60-80 ℃ of time of reacting is 4-6 hour, and 120-140 ℃ of time of reacting is 4-6 hour, and 160-250 ℃ of time of reacting is 12-24 hour.
10. claim 6 or the 7 described polybenzimidazole polymers application in preparation polybenzimidazole film, polybenzimidazole/phosphoric acid composite proton exchange membrane material, separatory membrane, transmitter, high-temperature fibre, high temperature resistant composite and binding agent.
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