CN111718503B - Proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole and preparation method thereof - Google Patents
Proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole and preparation method thereof Download PDFInfo
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- C08G73/18—Polybenzimidazoles
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Abstract
The invention discloses a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole and a preparation method thereof, wherein the structural formula of the proton exchange membrane material is as follows:
Description
Technical Field
The invention relates to the technical field of proton exchange membrane materials, in particular to a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole and a preparation method thereof.
Background
Polybenzimidazole (PBI) is a high polymer containing imidazole groups in molecular chains, and has good application prospect in the field of proton exchange membranes due to high glass transition temperature, good chemical stability and mechanical stability. PBI does not have groups capable of transferring protons, but can obtain certain proton conductivity after acid doping, and imidazole groups under an acidic condition can be protonated to carry positive charges, so that cross permeation of vanadium ions can be effectively prevented. PBI is a functional material with excellent stability and mechanical property, and is widely applied to the fields of hydrogen fuel cell automobiles and the like.
The preferred material in the field of high temperature fuel cells is polybenzimidazoles. The polybenzimidazole proton exchange membrane which is activated by doping phosphoric acid can still keep higher proton conductivity under the anhydrous state of 160 ℃, and simultaneously maintain better stability and catalyst compatibility, so the polybenzimidazole proton exchange membrane is considered as a high-temperature fuel cell exchange membrane material with the most bright prospect. In the high-temperature fuel cell operation test, the phosphoric acid loss phenomenon is found, so that the proton conductivity of the membrane cannot be kept at a stable level to operate, and a certain degree of reduction occurs. Meanwhile, the common commercial polybenzimidazole in the market is mostly obtained by polycondensation of biphenyl tetramine based on a rigid structure, so that the solubility of the polymer is poor, and the popularization and further development of the polybenzimidazole in the field of high-temperature proton exchange membranes are limited.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole and a preparation method thereof.
The inventors have found that calixarenes (calixarenes) have a cup-like shape, and are cyclic oligomers formed by connecting several phenol units in the ortho position to the phenolic hydroxyl group via methylene groups or heteroatoms (e.g., oxygen, sulfur, nitrogen, etc.). Although the calixarene has a small cavity, specific functional derivatization (e.g., sulfonation, phosphorylation, amination, etc.) can be performed at its upper edge, after which the calixarene can specifically bind to many objects (e.g., cations, anions, neutral molecules, etc.) and further mimic electrochemical processes. Sulfonated calixareneThere are structural advantages, including a characteristic electron-rich cavity, which can act as a channel or "corridor" for the passage of protons. The other is the function of the sulfonic acid group with hydrophilic upper edge, so the sulfonated calixarene has stronger bonding capability with objects such as organic cations and the like, the bonding capability of the sulfonated calixarene is very good, and the bonding capability of the sulfonated calixarene and part of the objects in water can reach 10 6 M -1 。
According to the invention, sulfonated calixarene is grafted to polybenzimidazole, a proton exchange membrane material with a structural formula shown as compound 13 is designed, the rigidity of polybenzimidazole is utilized to solve the strength problem of a proton membrane, the sulfonated structure of calixarene is utilized to solve the conductivity problem of the proton membrane, and an electron-rich structure model in calixarene is utilized to provide a channel for proton transfer and well solve the problem of large-scale proton transfer.
The technical scheme of the invention is as follows:
the invention provides a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole, wherein the structural formula of the proton exchange membrane material is as follows:
c has any one of the following structural formulas:
wherein R = CH 3 、C 2 H 5 、C 3 H 7 Or C 4 H 9 ；
C is connected to
At any substitutable position on the phenyl ring.
The invention provides a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole, wherein the structural formula of the proton exchange membrane material is as follows:
wherein n is an integer between 5000 and 10000.
The invention provides a preparation method of a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole, which comprises the following steps:
preparing aromatic tetramine monomers;
carrying out grafting reaction on the aromatic tetramine monomer and the hydroxyl calixarene to obtain a hydroxyl calixarene grafted tetramine monomer;
performing alkylation reaction on the hydroxyl calixarene grafted tetramine monomer to obtain an alkylated calixarene grafted tetramine monomer;
performing sulfonation reaction on the alkylated calixarene grafted tetramine monomer to obtain a sulfonated calixarene grafted tetramine monomer;
carrying out polymerization reaction on the sulfonated calixarene grafted tetramine monomer and terephthalic acid to obtain sulfonated calixarene grafted polybenzimidazole, namely the proton exchange membrane material;
wherein the structural formula of the aromatic tetramine monomer is shown as follows:
the structural formula of the hydroxyl calixarene is shown as follows:
the structural formula of the hydroxyl calixarene grafted tetramine monomer is as follows:
the structural formula of the alkylated calixarene grafted tetramine monomer is shown as follows:
the structural formula of the sulfonated calixarene grafted tetramine monomer is shown as follows:
the structural formula of the sulfonated calixarene grafted polybenzimidazole is shown as follows:
further, the step of performing a grafting reaction on the aromatic tetraamine monomer and the hydroxyl calixarene to obtain the hydroxyl calixarene-grafted tetraamine monomer specifically includes:
dissolving hydroxyl calixarene and sodium methoxide in acetonitrile, uniformly stirring to obtain a mixed solution, and then heating until the mixed solution becomes clear to obtain a clear solution;
adding an aromatic tetramine monomer into the clarified liquid, and carrying out a grafting reaction to obtain the hydroxyl calixarene grafted tetramine monomer.
Further, the step of performing alkylation reaction on the hydroxyl calixarene grafted tetramine monomer to obtain an alkylated calixarene grafted tetramine monomer specifically includes:
dissolving the hydroxyl calixarene grafted tetramine monomer in N, N-dimethylformamide, uniformly stirring, adding sodium hydride for reaction, and continuing to react for 1 hour after no gas is generated;
adding 1-bromobutane into the reaction system, stirring for 2 hours, then heating to 90 ℃, and reacting for 24 hours to obtain the alkylated calixarene grafted tetramine monomer.
Further, the step of performing a sulfonation reaction on the alkylated calixarene grafted tetramine monomer to obtain a sulfonated calixarene grafted tetramine monomer specifically includes:
dissolving a tetra-amine monomer grafted by alkylated calixarene in chloroform, stirring to obtain a tetra-amine monomer solution grafted by alkylated calixarene, and reacting the tetra-amine monomer solution grafted by alkylated calixarene in an ice bath environment to obtain a first reaction solution;
mixing chlorosulfonic acid and trichloromethane, stirring uniformly, adding into the first reaction solution, and reacting to obtain a second reaction solution;
removing liquid in the second reaction liquid, and dissolving the obtained solid in ethanol to obtain a solid solution;
and dropwise adding an ethanol solution of sodium hydroxide into the solid solution for reaction to obtain the sulfonated calixarene grafted tetramine monomer.
Further, the step of performing a polymerization reaction on the sulfonated calixarene-grafted tetramine monomer and terephthalic acid to obtain the sulfonated calixarene-grafted polybenzimidazole specifically comprises:
mixing polyphosphoric acid and P 2 O 5 Mixing and stirring under inert atmosphere until a transparent clear solution is obtained;
and adding a sulfonated calixarene grafted tetramine monomer and terephthalic acid into the transparent clear solution to carry out polymerization reaction, thereby obtaining the sulfonated calixarene grafted polybenzimidazole.
Still further, the polymerization conditions include: the reaction was carried out at 90 ℃ for 3 hours, at 130 ℃ for 3 hours and at 200 ℃ for 10 hours with stirring.
Has the beneficial effects that: the proton exchange membrane material provided by the invention has the following advantages:
1. the synthesis process is simple and the cost is low;
2. the product has an inner salt structure, and can transfer protons or hydroxide ions or simultaneously transfer two ions (anions and cations) without acidification or alkalization;
3. the prepared proton exchange membrane has good ion conductivity due to the internal salt structure, so that the proton exchange membrane has good conductivity;
4. the mechanical strength is high, and the polybenzimidazole structure enables molecules to have a strong rigid structure, so that the proton exchange membrane has good mechanical strength;
5. the requirements on temperature and humidity are not high, and the polymerization degree of molecules is high enough, so that the temperature and humidity dependence is small, and the device can normally work in a wider temperature and humidity range;
6. the electron-rich channel of the calixarene can well transfer protons or other acidic cations, the transfer direction of ions is limited, and the proton exchange membrane has unicity, so that the conductivity of the prepared proton exchange membrane is greatly enhanced.
Detailed Description
The invention provides a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole and a preparation method thereof, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The present invention is described in detail below with reference to specific examples.
(1) Synthesis of Compound 2 (Hydroxycalixarene)
The preparation of compound 2 (hydroxycitric) from compound 1 (p-tert-butylcalixarene) is described in detail in the reference: zheng wenjun. Supramolecular self-assembly based on calixarene and binaphthol [ master paper ]. Qingdao: qingdao university of science and technology 2019.
(2) Preparation of Compound 5 (N- (4-acetyl-2-nitrophenyl) acetamide)
Methods for preparing compound 5 are described in the references: liu, J.G, wang, L.F, yang, H.X, li, H.S., li, Y.F, fan, L.and Yang, S.Y.Synthesis and catalysis of new polybenzimidazole, polymer Science Part A, polymer chemistry.2004,42 (8): 1845-1856.
(3) Preparation of Compound 7
A2000 ml three-necked flask was taken, equipped with a reflux condenser, and compound 5 (133.2g, 0.6 mol), compound 6 (p-benzylbromobenzaldehyde, 59.7g,0.3 mol), ammonium acetate (3.9mol, 300g) were dissolved in 800ml of glacial acetic acid, and the mixture was heated to boiling with stirring, refluxed and condensed for 3 hours, cooled to give a yellow solid precipitate, filtered, and washed with water to give a crude product, which was recrystallized from ethanol to give 90.4g of compound 7.
1 H NMR(400MHz，CDCl 3 ):δ＝9.09(s,2H),8.65(d,2H),8.20(s,2H),8.10(d，2H)，7.41-7.47(m，4H),4.56(s，2H),2.03(s，6H)；MS(EI)m/z 603.08(M+)。
(4) Preparation of Compound 9 (aromatic Tetramine monomer)
Dissolving 15g of KOH in 50ml of methanol, dissolving a compound 7 (44.83g, 77.36mmol) in 500ml of methanol, dropwise adding the methanol solution of the compound 7 into the methanol solution of the KOH under the condition of vigorous stirring, controlling the dropwise adding time to be about 0.5 hour, after the dropwise adding is finished, adding 10g of KOH into the reaction mixture, reacting the reaction mixture for 6 hours under the heating reflux state, cooling to room temperature, then pouring the reaction mixture into 1000ml of deionized water to obtain yellow solid precipitate, collecting the precipitate, washing with water, and then drying under vacuum for 12 hours to obtain a compound 8.
Adding 150ml of ethanol into a 250ml three-neck flask as a solvent, dissolving a compound 8 (4.95g, 0.01mol) in the ethanol, adding 0.24g of 5% palladium carbon (Pd/C) as a catalyst, heating the mixture solution to slight boiling, dissolving 15ml of hydrazine hydrate in 30ml of ethanol, dropwise adding the ethanol solution of the hydrazine hydrate into the reaction mixture, continuously heating and refluxing for 24 hours after the dropwise addition is finished, then filtering to remove the palladium carbon while hot, cooling to separate out light yellow crystalline solid, filtering and collecting the solid, washing with water, and drying in vacuum to obtain 3.12g of a compound 9.
1 H NMR(400MHz，CDCl 3 ):δ＝8.20(s,2H),7.47(d,4H),7.41(d,2H),7.13(s，2H)，6.84(d，2H),4.56(s，2H)；MS(EI)m/z 459.11(M+)。
(5) Preparation of Compound 10 (Hydroxycalixarene-grafted Tetramine monomer)
A500-mL dry three-neck round-bottom flask was charged with weighed compound 2 (3.4 g,8 mmol) and sodium methoxide (0.54g, 10 mmol) in that order, and 100mL of anhydrous acetonitrile was added by syringe under nitrogen. After stirring the mixture at room temperature, the mixture was refluxed for 1 hour, whereupon the suspension in the reaction flask became clear, heating was stopped, the mixture was cooled to room temperature, and then compound 9 (1.84g, 4 mmol) was added to the reaction flask. Refluxing was continued for 24 hours. And cooling to room temperature after the reaction is finished, filtering to remove the solid, washing the filter cake with a small amount of acetonitrile, collecting the filtrate, and spin-drying the filtrate to obtain a white solid. Separating with 500ml separating funnel, adding anhydrous sodium sulfate into organic phase, stirring, drying, filtering, spin drying organic phase, and recrystallizing the crude product with ethanol to obtain compound 10.
1 H NMR(400MHz，CDCl 3 ):δ＝8.20(s,2H),7.47(d,4H),7.41(d,2H),7.19(m，1H)，7.07--7.08(m，5H),6.91(m，5H),6.84(d，2H),5.16(s，2H),3.81(s，8H)；MS(EI)m/z 803.35(M+)。
(6) Preparation of Compound 11 (alkylated calixarene grafted Tetramine monomer)
A dry 250ml round bottom three-necked flask was taken, compound 10 (3.3 g, 4.1mmol) was added to the flask, then 100ml of anhydrous DMF was added by syringe, after stirring well, sodium hydride (1.8g, 75mmol) was added in portions to react to generate a large amount of gas, at which time the solution became off-white turbid, after no more gas was generated, the reaction was continued for 1 hour, and then 1-bromobutane (2.74g, 20mmol) was slowly added dropwise. After the dropwise addition, the solution turns from colorless to orange yellow, the stirring is continued for 2 hours at room temperature, the solution is heated to 90 ℃ under oil bath, and the reaction is carried out for 24 hours. After the reaction bottle is cooled to room temperature, white solid is separated out from a brown reaction system and is gathered at the bottom of the bottle. And (2) performing suction filtration by using a Buchner funnel, spin-drying the obtained filtrate, and separating by using a column chromatography method, wherein an eluent is petroleum ether with the volume ratio of 5: dichloromethane to obtain white solid compound 11.
1 H NMR(400MHz，CDCl 3 ):δ＝8.20(s,2H),7.47(d,4H),7.41(d,2H),7.19(m，4H)，7.13(s，2H),7.08(d，8H),6.84(d，2H),5.16(s，2H),4.08(t，6H)，3.81(s，8H),1.74(m，6H),1.47(m，8H),0.96(t，9H)；MS(EI)m/z 971.53(M+)。
(7) Preparation of Compound 12 (sulfonated calixarene grafted Tetramine monomer)
A dry 250ml three-neck round-bottom flask was taken under inert gas, weighed amount of compound 11 (1.26g, 1.3 mmol) was added to the flask, 50ml of anhydrous chloroform was added to the flask, the solid was dissolved completely by stirring, and the flask was placed in an ice-water bath and allowed to react for 30 minutes. And (3) taking another dry beaker, transferring 0.5ml of chlorosulfonic acid by using a transfer pipette, adding 60ml of anhydrous trichloromethane, uniformly stirring, transferring the trichloromethane solution of the chlorosulfonic acid into a dropping funnel, slowly dropping into the reaction solution, and controlling the dropping speed to ensure that the dropping process is over 30 minutes. The solution slowly turns wine red, after the dropwise addition, the ice bath is removed, the temperature is slowly raised to room temperature, and the reaction is carried out for 3 hours to obtain a red transparent reaction solution. The reaction solution was spin-dried to obtain a black solid, and 100ml of absolute ethanol was added to the reaction flask to dissolve the solid. While stirring, 360mg of sodium hydroxide was dissolved in 70ml of ethanol, and the resulting ethanol solution of sodium hydroxide was added dropwise to the reaction solution, and a large amount of white flocculent solid was found to precipitate, and the reaction was continued for 30 minutes. Standing for layering, performing suction filtration by using a Buchner funnel to obtain a white solid, dissolving the obtained white solid with a small amount of water, adding ethanol for recrystallization, and performing vacuum drying to obtain a white solid compound 12.
1 H NMR(400MHz，DMSO-d6):δ＝8.20(s,2H),7.62(s,8H),7.47(d,4H),7.41(d,2H),7.13(s，2H)，7.13(s，2H),6.84(d，2H),5.16(s，2H),4.06(t，6H),3.81(s，8H),1.74(m，6H),1.47(m，8H),0.96(t，9H)；MS(EI)m/z 1379.29(M+)。
(8) Preparation of Compound 13 (sulfonated calixarene-grafted polybenzimidazole)
40.0g PPA (80%) and 10.0g P 2 O 5 Adding into 250ml three-neck round-bottom flask equipped with stirrer and gas-guide tube, and deoxygenating under nitrogen protection at 140 deg.C under stirring until P 2 O 5 The white powder completely dissolved to a clear and clear solution (P) 2 O 5 84%) was cooled to room temperature under nitrogen. Adding sulfonated calixarene-containing tetramine compound 12 (5.93g, 4.3mmol) and terephthalic acid TPA (0.72g, 4.3mmol), N-N at RT 2 After about 15min, the mixture was stirred at 90 ℃ for 3 hours, at 130 ℃ for 3 hours, and at 200 ℃ for 10 hours to obtain a dark viscous solution after the reaction. After cooling to 140 ℃, the viscous solution is poured into deionized water to precipitate a block polymer. Mechanical stirring is adopted in the whole reaction process. Then pouring the polymer into a resin pulper, crushing, finally repeatedly soaking and washing the obtained product in distilled water to remove redundant acid, filtering, and drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain a brown yellow target product compound 13.
1 H NMR(400MHz，DMSO-d6):δ＝8.60(d,2H),8.58(d,2H),8.43(s,2H),7.76(d,2H),7.62(s,8H),7.47(d，2H)，7.45(d,2H),5.16(s，2H),4.06(t，6H),3.81(s，8H),1.74(m，6H),1.47(m，8H),0.96(t，9H)。
(9) Preparation and Performance testing of proton exchange membranes
The compound 13 (i.e. proton exchange membrane material) prepared above is dissolved in DMSO solvent to obtain a proton exchange membrane material solution. The filtered proton exchange membrane material solution was then poured onto an ultra-flat petri dish and dried for 24 hours to give a tan transparent polymer membrane (thickness 70 μm). The polymer membrane was peeled off, rinsed with distilled water, and immersed in a hydrochloric acid solution to convert it into an acid type proton exchange membrane.
a. The existence of the high-stability benzimidazole structure improves the thermal stability, oxidation resistance stability and mechanical property of the compound 13 to a certain extent, does not crack in Fenton reagent for 120h, and has the tensile strength of between 10.14 and 89MPa and the thermal decomposition temperature of more than 300 ℃.
b. The proton conductivity of the membrane prepared by the compound 13 can reach 0.082S.cm under the anhydrous state at 180 DEG C -1 Is superior to the prior Nafion membrane.
In summary, the proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole and the preparation method thereof provided by the invention have the following advantages: 1. the synthesis process is simple and the cost is low; 2. the ion exchanger has an inner salt structure, can transmit protons or hydroxide ions or simultaneously transmit two ions (anions and cations) without acidification or alkalization; 3. the proton exchange membrane has good conductivity, and the inner salt structure ensures that the prepared proton exchange membrane has good ion conductivity so as to have good conductivity; 4. the mechanical strength is high, and the polybenzimidazole structure enables molecules to have a strong rigid structure, so that the proton exchange membrane has good mechanical strength; 5. the requirements on temperature and humidity are not high, and the normal operation can be carried out within a wider temperature and humidity range as long as the polymerization degree of molecules is high enough and the dependence on the temperature and the humidity is small; 6. the electron-rich channel of the calixarene can well transfer protons or other acidic cations, the transfer direction of ions is limited, and the proton exchange membrane has unicity, so that the conductivity of the prepared proton exchange membrane is greatly enhanced.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. The proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole is characterized in that the structural formula of the proton exchange membrane material is as follows:
wherein n is an integer between 5000 and 10000.
2. A method for preparing a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole according to claim 1, comprising the steps of:
preparing aromatic tetramine monomer;
carrying out a grafting reaction on the aromatic tetramine monomer and the hydroxyl calixarene to obtain a hydroxyl calixarene grafted tetramine monomer;
performing alkylation reaction on the hydroxyl calixarene grafted tetramine monomer to obtain an alkylated calixarene grafted tetramine monomer;
performing sulfonation reaction of grafted calixarene on the alkylated calixarene grafted tetramine monomer to obtain a sulfonated calixarene grafted tetramine monomer;
carrying out polymerization reaction on the sulfonated calixarene grafted tetramine monomer and terephthalic acid to obtain sulfonated calixarene grafted polybenzimidazole, namely the proton exchange membrane material;
wherein the structural formula of the aromatic tetramine monomer is shown as follows:
the structural formula of the hydroxyl calixarene is shown as follows:
the structural formula of the hydroxyl calixarene grafted tetramine monomer is as follows:
the structural formula of the alkylated calixarene grafted tetramine monomer is shown as follows:
the structural formula of the sulfonated calixarene grafted tetramine monomer is shown as follows:
the structural formula of the sulfonated calixarene grafted polybenzimidazole is shown as follows:
3. the method for preparing the proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole according to claim 2, wherein the step of performing a grafting reaction on the aromatic tetramine monomer and the hydroxyl calixarene to obtain the hydroxyl calixarene grafted tetramine monomer specifically comprises:
dissolving hydroxyl calixarene and sodium methoxide in acetonitrile, uniformly stirring to obtain a mixed solution, and then heating until the mixed solution becomes clear to obtain a clear solution;
adding an aromatic tetramine monomer into the clarified liquid, and carrying out a grafting reaction to obtain the hydroxyl calixarene grafted tetramine monomer.
4. The method for preparing a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole according to claim 2, wherein the step of performing alkylation reaction on the hydroxyl calixarene-grafted tetramine monomer to obtain the alkylated calixarene-grafted tetramine monomer specifically comprises:
dissolving the hydroxyl calixarene grafted tetramine monomer in N, N-dimethylformamide, uniformly stirring, adding sodium hydride for reaction, and continuing the reaction for 1 hour after the reaction is carried out until no gas is generated;
adding 1-bromobutane into the reaction system, stirring for 2 hours, then heating to 90 ℃, and reacting for 24 hours to obtain the alkylated calixarene grafted tetramine monomer.
5. The method for preparing a proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole according to claim 2, wherein the step of performing sulfonation reaction on the alkylated calixarene-grafted tetramine monomer to obtain a sulfonated calixarene-grafted tetramine monomer specifically comprises:
dissolving a tetraamine monomer grafted by alkylated calixarene in chloroform, stirring to obtain a tetraamine monomer solution grafted by alkylated calixarene, and reacting the tetraamine monomer solution grafted by alkylated calixarene in an ice bath environment to obtain a first reaction solution;
mixing chlorosulfonic acid and trichloromethane, stirring uniformly, adding into the first reaction solution, and reacting to obtain a second reaction solution;
removing liquid in the second reaction liquid, and dissolving the obtained solid in ethanol to obtain a solid solution;
and dropwise adding an ethanol solution of sodium hydroxide into the solid solution for reaction to obtain the sulfonated calixarene grafted tetramine monomer.
6. The method for preparing the proton exchange membrane material of sulfonated calixarene grafted polybenzimidazole according to claim 2, wherein the step of polymerizing the sulfonated calixarene-grafted tetramine monomer and terephthalic acid to obtain the sulfonated calixarene-grafted polybenzimidazole specifically comprises:
mixing polyphosphoric acid and P 2 O 5 Mixing, stirring under inert atmosphere until obtaining transparent clear solution;
and adding a sulfonated calixarene grafted tetramine monomer and terephthalic acid into the transparent clear solution to carry out polymerization reaction, thereby obtaining the sulfonated calixarene grafted polybenzimidazole.
7. The method of claim 6, wherein the polymerization conditions comprise: the reaction was carried out at 90 ℃ for 3 hours, at 130 ℃ for 3 hours and at 200 ℃ for 10 hours with stirring.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220162A (en) * | 2007-12-06 | 2008-07-16 | 上海交通大学 | Production method for 2 or multi-halohydrocarbon crosslinked polybenzimidazole crosslinked membrane |
| JP2013101841A (en) * | 2011-11-09 | 2013-05-23 | Univ Of Tokyo | Heat resistant polymer electrolyte membrane and method for manufacturing the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220162A (en) * | 2007-12-06 | 2008-07-16 | 上海交通大学 | Production method for 2 or multi-halohydrocarbon crosslinked polybenzimidazole crosslinked membrane |
| JP2013101841A (en) * | 2011-11-09 | 2013-05-23 | Univ Of Tokyo | Heat resistant polymer electrolyte membrane and method for manufacturing the same |
Non-Patent Citations (2)
| Title |
|---|
| Thermally crosslinked sulfonated polybenzimidazole membranes and their performance in high temperature polymer electrolyte fuel cells;N.Nambi Krishnan等;《Journal of Membrane Science》;20191231;第588卷 * |
| 聚苯并咪唑在高温质子交换膜燃料电池中的应用研究进展;徐帆等;《化工新型材料》;20121215(第12期) * |
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