CN111205465B - Preparation method and application of poly (diphosphophosphazene) high-temperature proton conductor - Google Patents

Preparation method and application of poly (diphosphophosphazene) high-temperature proton conductor Download PDF

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CN111205465B
CN111205465B CN202010028561.8A CN202010028561A CN111205465B CN 111205465 B CN111205465 B CN 111205465B CN 202010028561 A CN202010028561 A CN 202010028561A CN 111205465 B CN111205465 B CN 111205465B
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diphosphophosphazene
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CN111205465A (en
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李忠芳
王传刚
孙鹏
郭辉
王素文
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Shandong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025—Polyphosphazenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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Abstract

The invention relates to a preparation method of a poly (diphosphonate phosphazene) high-temperature-resistant proton conductor. Carrying out ring-opening polymerization on a proper amount of Hexachlorocyclotriphosphazene (HCCP) in diphenyl ether at the temperature of 210-250 ℃ to obtain poly (dichlorophosphazene) (PDCP) and reacting with phosphite triester to obtain poly (bis (dialkoxy phosphate) phosphazene) (PBPP); hydrolyzing PBPP with concentrated salt to obtain poly (diphosphonithosphazene) (PDPP), and polymerizing PDPP and one or more of high-valence metal ions to obtain water-insoluble high-temperature-resistant white solid MPDPP of proton conductor. The high-temperature-resistant proton conductor can be used in the fields of solid acid catalysts, sensors, fuel cell proton conducting materials and the like.

Description

Preparation method and application of poly (diphosphophosphazene) high-temperature proton conductor
Technical Field
The invention relates to a preparation method and application of a poly (diphosphonate phosphazene) high-temperature-resistant proton conductor. It can be used as acid catalyst in chemical production, biodiesel preparation and other fields, and can be used as solid acid in sensor, fuel cell and other fields.
Technical Field
Inorganic phosphate generally has good thermal stability, wherein hydroxyl which does not participate in bonding shows certain acidity, can form hydrogen bond and ionize to generate proton, can also participate in ion exchange, and has wide application.
The hydrogen phosphate of many metals has good thermal stability, wherein the exposed hydroxyl can ionize proton, shows certain acidity, and can be used as proton conductor in the fields of electrolysis, electrochemical sensing, fuel cells and the like, and the metals comprise cesium, zirconium, tin, titanium and the like [ ZL 100421291C; ZL 102770198B ]. Wherein, the dihydrogen phosphate of cesium, rubidium and the like can undergo super proton phase transition at a certain temperature, namely, the structure is rearranged when the transition temperature is reached, which is beneficial to forming hydrogen bonds and improving the acidity. The hydrogen phosphate of zirconium, titanium, etc. does not undergo a super-proton phase transition, has a strong water absorption property and a layered structure, and exhibits acidity depending on exposed hydroxyl groups. Hydrogen phosphates of potassium, lithium, etc. decompose at higher temperatures.
The organic phosphonic acid and the salt thereof have extremely important application in the fields of proton conduction, acid catalysis, water treatment and the like. The metal salt is mostly insoluble in water (except lithium, sodium, potassium and ammonium salt), has good thermal stability, and the exposed hydroxyl is easy to form hydrogen bond, and has certain acidity and ion exchange capacity.
The organic phosphonates are generally prepared from organic phosphonic acids and water-soluble salts in an aqueous phase.
The key to the preparation of organic phosphonic acid lies in the construction of C-P bond. The phosphorus source may be highly reactive phosphorus trichloride [ Fields E K, Journal of the American Chemical Society (Proc. Natl. Chem.), (1952, 74, 1528) -1531] or phosphorus oxychloride [ ZL1524864 and ZL105859771], but phosphorus trichloride and phosphorus oxychloride are very susceptible to hydrolysis, have high requirements for reaction equipment and reagents, and have certain toxicity, contamination and corrosivity, and are therefore not suitable for mass production.
Phosphorous acid can react with halogenated hydrocarbons, epoxy compounds, etc. to produce organic phosphonic compounds [ ZL105884938 ]. The reaction condition is mild, and the operation is simple. However, phosphorous acid is easily oxidized to phosphoric acid in air and loses reactivity, so that inert gas shielding is often required during use.
The phosphite ester and the epoxy resin can react under the catalysis of Lewis acid to prepare organic phosphonate ester [ Sobhani S, et al. tetrahedron, 2009,65, 7691-; after hydrolysis, Sardarian A R, et al synthetic Communications, 2007,37,289 and 295, the organic phosphonic acid is obtained.
Phosphite ester and sultone can directly react to prepare sulfonic alkyl phosphonate ester, and sulfonic alkyl phosphonic acid is obtained after hydrolysis [ US 2957905 ]. Due to the introduction of sulfonic acid groups, the compounds often have strong acidity and ion exchange capacity, but the sulfonic acid groups are easy to remove at high temperature, so the temperature resistance of the compounds is limited.
Phosphites and halogenated hydrocarbons can be reacted to prepare phosphonates, known as the Arbuzov reaction. The method has the advantages of mild conditions, low cost, wide application range and no need of gas protection and catalysis, thereby being a common method for preparing the phosphonate. The phosphonate is hydrolyzed and then reacts with soluble salt in the water phase to prepare the organic phosphonate.
Patent document CN 201610893595.7 Liuyan and the like disclose a preparation method of a sulfonated polyphosphazene/ether ketone proton exchange membrane material, which has the characteristics of low preparation cost, high conductivity, good alcohol resistance, good oxidation resistance, good heat resistance and the like; CN201811558269.6 Wu Zhanpeng and the like disclose a flame-retardant degradable polyphosphazene type epoxy resin and a preparation method thereof, so that the fracture form of the prepared epoxy resin is shown as certain toughness fracture, and the defect of poor toughness of the cured product of the traditional epoxy resin is structurally solved.
The invention content is as follows:
the invention utilizes strong polar bond between P-Cl in poly (dichlorophosphazene) macromolecule to react with phosphite ester to obtain poly (diphosphonite), hydrolyzes in concentrated hydrochloric acid to obtain poly (diphosphonite), and reacts with water-soluble high-valence transition metal ion to obtain insoluble poly (diphosphonite) polymer. The specific operation steps and reaction process are as follows:
(1) preparation of polyphosphazene diphosphate proton conductor
Under the protection of nitrogen, respectively adding sulfamic acid (0.52mmol, 0.05g), Hexachlorocyclotriphosphazene (HCCP) (14.4mmol, 5g) and solvent diphenyl ether (15-30 mL) into a three-neck flask provided with a stirrer and a condenser, introducing nitrogen for 20-40 min, stirring, heating to 210-250 ℃ for ring-opening polymerization, stopping heating when the solution becomes viscous, cooling, pouring into a petroleum ether beaker containing 40-60 mL to remove unreacted raw material HCCP, washing with petroleum ether for three times, carrying out suction filtration, and drying the obtained solid product in a vacuum drying oven at 70-90 ℃ for 4-8 h to obtain poly (dichlorophosphazene) (PDCP); reacting the obtained poly (dichlorophosphazene) with excessive (50-60 mL) triethyl phosphite for 5-7 h at 100-120 ℃, cooling, washing with a proper amount of petroleum ether for 3-4 times to remove excessive unreacted triethyl phosphite, performing suction filtration, and drying the solid in a vacuum drying oven at 60-100 ℃ to obtain poly (bis (diethoxyphosphate) phosphazene) (PBPP); adding 60-90 mL of concentrated hydrochloric acid into the obtained poly (bis (diethoxyphosphate) phosphazene) (PBPP), hydrolyzing at 110-150 ℃ under stirring until the solution becomes clear, concentrating at 110-140 ℃ until the solution is nearly dry to remove reaction products and excessive concentrated hydrochloric acid, extracting for 3-4 times by using 30-50 mL of ethyl acetate to remove unhydrolyzed and complete PBPP, and drying the residual liquid in a vacuum drying oven at 110-130 ℃ to obtain poly (diphosphophosphazene) (PDPP), wherein the equation of the reaction process is as follows.
Figure GDA0003130899980000031
Dissolving 2.07g of the obtained white solid poly (diphosphonite) (PDPP) in certain deionized water, dissolving 1.61g of zirconium oxychloride in dilute hydrochloric acid, dropwise adding the zirconium oxychloride solution into the aqueous solution of poly (diphosphonite) (PDPP) while stirring until the zirconium oxychloride and the dilute hydrochloric acid are completely dissolved, stirring for 24 hours after the zirconium oxychloride and the dilute hydrochloric acid are completely dissolved, performing suction filtration, washing with water to be neutral, and drying in a vacuum drying oven at 80-90 ℃ to obtain 1.93g of white solid ZrPDPP (0.78) (the mass percentage of the white solid is zirconium oxychloride: PDPP is 0.78), wherein the yield is 76.44%. ZrPDPP with different proportions can be obtained by the method.
Figure GDA0003130899980000032
If zirconium ions are replaced by other metal ions, MPDPP salts of other transition metal ions can be obtained, where Mn+＝Zr4+、Ce4+、Fe3+、Co3+、La3+Or Y3+
Poly (phosphazene diphosphate) (MPDPP) is characterized by:
MPDPP is a phosphate of a three-dimensional polymer type formed by a polyphosphoric acid group and a high-valence metal ion in a polyphosphazene inorganic polymer, and a salt thereof may be insoluble when the amount of the metal ion is a certain ratio, but an excess phosphate group or a residual hydroxyl group in the phosphate group in a molecule may ionize a proton, and thus, the salt is an acidic proton conductor, and the salt has high temperature resistance (no decomposition at 400 ℃), and thus, the salt has wide applications: for example, it can be used as a solid acid for acid-catalyzed reactions such as esterification, transesterification, and the like. Can be used in the fields of esterification reaction, hydrolysis reaction, biodiesel preparation and the like; the salt is high temperature resistant, has excellent proton conductivity at high temperature and low humidity, and can be used for preparing a high-temperature proton exchange membrane by using a proton conductor additive; can prevent the water from being taken away and lost, thereby greatly improving the durability of the proton exchange membrane; although the polyphosphazene is an inorganic high polymer material, the polyphosphazene can be dissolved in an organic solvent and has good compatibility with an organic high polymer material, so that the polyphosphazene has good compatibility when added into the organic high polymer material and does not have a phase separation phenomenon.
The innovation points of the invention are as follows:
1) the selected polyphosphazenes belong to inorganic high polymer materials, and have good compatibility with organic solvents and high temperature resistance.
2) The intermediate PDPP is a polymer with a polyphosphate group, and because the phosphate group content is very high, a plurality of residual phosphate groups or hydroxyl groups in the phosphate groups can be contained in the insoluble salt molecules of the high-valence transition metal; the molecules can ionize to form protons, have acidity, and can also play a role in proton conduction even under low humidity or dry conditions. Thus, solid acid catalysts useful in organic reactions; proton exchange membranes or membrane electrodes for use at high temperatures and low humidity.
(2) Preparation of poly (phosphonitrile diphosphonate) proton conductor polybenzimidazole proton exchange membrane
Adding 1.00g of mPBI (mPBI) into 10mL of N, N-dimethylacetamide (DMAc), magnetically stirring at 110-140 ℃, completely dissolving for 4-6 h, cooling to 50-70 ℃, adding 0.0526g of epoxy resin (TGDDM), stirring for 0.5-1 h, adding 1.2082g of ZrPDPP, stirring for 1-3 h to uniformly disperse, ultrasonically shaking to remove bubbles, transferring to a tiled glass plate (with raised edges on four sides), heating to 50-70 ℃ in a vacuum drying oven, casting for 6-9 h, heating to 150-170 ℃, keeping the temperature for 5-8 h, fully crosslinking, cooling to 110-130 ℃, keeping the temperature for 4-5 h, cooling to room temperature, and soaking a film in water. The prepared film was labeled: mPBI-TGDDM (5%)/ZrPDPP (50%).
In the same way, varying the mass of TGDDM and ZrPDPP gives a series of mPBI-TGDDM (x)/ZrPDPP (y) crosslinked membranes, where x and y are the weight percentages of TGDDM and ZrPDPP, respectively.
Other PBI-TGDDM (x)/ZrPDPP (y) crosslinked membranes can be obtained by the same method, replacing mPBI with other PBI. In the same way, the TGDDM is replaced by other cross-linking agents, and the composite proton exchange membrane cross-linked by other cross-linking agents can be obtained. The structure of the composite membrane is as follows:
Figure GDA0003130899980000051
(3) preparing and assembling a membrane electrode of a high-temperature proton exchange membrane fuel cell and testing the performance of the cell. The membrane electrode is prepared according to the traditional method and process, a single cell is assembled by the membrane electrode and is connected to a fuel cell test system for testing, hydrogen with the relative humidity of 30 percent is used as fuel for the anode, the flow rate is 40mL/min, the working temperature of the cell is 250 ℃, the oxygen flow rate of the cathode is 20mL/min, and the back pressure is 0.2 MPa. Before the cell performance test, activation is firstly carried out, the performance of the cell is tested, and MEA test of different membranes is carried out.
(4) For solid acid catalysts.
The method is used for solid acid catalyzed reactions such as esterification reaction, ester exchange reaction and the like. The preparation of biological dibutyl phthalate by reacting phthalic anhydride with butanol was studied, and the influence of catalytic reaction process conditions on yield was studied.
(5) A catalyst for use in a process for the production of biodiesel.
The research takes cottonseed oil as an example, researches MPDPP as a solid acid catalyst for catalytic reaction of cottonseed oil and ethanol, researches the influence of different MPDPP on catalytic performance, and researches reaction process conditions.
Detailed Description
[ example 1 ]: preparation of poly (dichlorophosphazene)
Under the protection of nitrogen, respectively adding sulfamic acid (0.52mmol, 0.05g), Hexachlorocyclotriphosphazene (HCCP) (14.4mmol, 5g) and solvent diphenyl ether (15-30 mL) into a three-neck flask provided with a stirrer and a condenser, introducing nitrogen for 20-40 min, stirring, heating to 210-250 ℃ for ring-opening polymerization, stopping heating when the solution becomes viscous, cooling, pouring into a petroleum ether beaker containing 40-60 mL to remove unreacted raw material HCCP, washing with petroleum ether for three times, carrying out suction filtration on the obtained solid product in a vacuum drying oven at 70-90 ℃ for 4-8 h to obtain poly (dichlorophosphazene) (PDCP), wherein the yield of the obtained PDCP is 70%, and the viscosity average molecular weight is 6-8 ten thousand
The method is adopted to only change diphenyl ether into other solvents (one or a mixture of a plurality of aromatic hydrocarbon solvent oil, sulfolane, glyceryl triacetate, pentaerythritol tetraacetate, polyethylene glycol diacetate, liquid paraffin and methyl naphthalene oil), can also control the temperature to be 210-250 ℃, can even control higher reaction temperature in some cases, can also obtain products of ring-opening polymerization, and only needs to use a solvent with better solvent solubility and low boiling point to clean when the solvent is removed.
The yield of ring-opening polymerization reaction by using different solvents is within the range of 40-80%, and the viscosity-average molecular weight is within the range of 4-10 ten thousand.
[ example 2 ]: preparation of poly (bis (dialkoxyphosphate) phosphazene) (PBPP)
Reacting 20g of the obtained poly (dichlorophosphazene) with excessive (50-60 mL) triethyl phosphite at 100-120 ℃ for 5-7 h, cooling, washing with a proper amount of petroleum ether for 3-4 times to remove excessive unreacted triethyl phosphite, performing suction filtration, and drying the solid in a vacuum drying oven at 60-100 ℃ to obtain poly (bis (diethoxyphosphate) phosphazene) (PBPP); the poly (bis (diethoxyphosphate) phosphazene) (PBPP) yield obtained was 83%. The yields of the reactions carried out with different phosphites or under different conditions using the same reaction procedure are summarized in table 1:
TABLE 1 reaction conditions and yields for the preparation of PBPP from different phosphite reactions
Figure GDA0003130899980000061
[ example 3 ]: preparation of poly (diphosphophosphazene) s
Adding 25g of PBPP into 60-90 mL of concentrated hydrochloric acid, hydrolyzing at 110-150 ℃ under stirring until the solution becomes clear, concentrating at 110-140 ℃ until the solution is nearly dry to remove reaction products and excessive concentrated hydrochloric acid, extracting for 3-4 times by using 30-50 mL of ethyl acetate to remove unhydrolyzed PBPP, and drying the residual liquid in a vacuum drying oven at 110-130 ℃ to obtain poly (diphosphophosphazene) (PDPP) with the yield of 89%
The same reaction procedure was followed except that extraction with dichloromethane, benzene, toluene or petroleum ether was used, and the yields were 87%, 83%, 81% and 85%, respectively.
The same reaction procedure was used, reflux 24h in concentrated hydrochloric acid, distillation at 70 ℃ under reduced pressure, extraction with ethyl acetate, 84% yield. The results of the hydrolysis reaction of PBPP with different ester groups are shown in Table 2.
TABLE 2 yield of PDPP prepared by hydrolysis of PBPP with different ester groups
Figure GDA0003130899980000071
[ example 4 ]: preparation of ZrPDPP (0.78)
Dissolving 2.07g of the obtained white solid of poly (diphosphophosphazene) (PDPP) in certain deionized water, dissolving 1.61g of zirconium oxychloride in dilute hydrochloric acid, dropwise adding the zirconium oxychloride solution into the aqueous solution of poly (diphosphophosphazene) (PDPP) while stirring until the zirconium oxychloride and the dilute hydrochloric acid are completely dissolved, after dropwise adding, stirring and reacting for 24 hours at room temperature, performing suction filtration, washing with water to be neutral, and drying at 80-90 ℃ in a vacuum drying oven to obtain 1.93g of white solid ZrPDPP (0.78), wherein the yield is 76.44%.
The mass ratio of zirconium oxychloride to PDPP was 0.78, and therefore, it was recorded as ZrPDPP (0.78).
The preparation method of other ZrPDPP with different molar ratios is the same as the above, except that the mass ratio of the zirconium oxychloride to the PDPP is shown in Table 3.
The preparation process conditions and properties of MPDPP with different mass ratios can be obtained by adopting other soluble salts of high-valence metal ions to replace zirconium oxychloride, and are shown in Table 3.
[ example 5 ]: proton conductivity test of ZrPDPP
ZrPDPP (0.78) is used as a proton conductor, and the proton conductivity reaches 0.159S/cm at 180 ℃ and 100% relative humidity; the proton conductivity reaches 0.081S/cm at 180 ℃ and 50% relative humidity; the proton conductivity reaches 0.00467S/cm under the dry condition at 180 ℃. The measured conductivities at different temperatures and at different relative humidities for the pressed sheets of the MPDPP salt prepared by replacing zirconium oxychloride with other soluble salts of higher valent metal ions are shown in table 4.
[ example 6 ]: MPDPP solid acid for catalyzing esterification reaction
Preparation of dibutyl phthalate was exemplified by the reaction of phthalic anhydride with butanol catalyzed by ZrPDPP (0.78). Adding 5.9g (0.04mol) of phthalic anhydride into a 100mL three-neck flask provided with a water separator, an electric stirring, a reflux condenser pipe and an oil bath kettle, adding 12.5mL (0.12mol, 2 g) of excessive n-butyl alcohol into ZrPDPP (0.78) and adding n-butyl alcohol into the water separator until branch pipes are flush, slowly heating to slightly boil the reaction mixture under stirring, continuously heating to reflux after about 15min, gradually evaporating azeotrope of n-butyl alcohol and water, condensing at the bottom of the water separator, gradually flowing small water beads to the bottom of the water separator, stopping heating when the reaction temperature is raised to 150 ℃, recording the volume of water in the water separator, performing suction filtration to remove a solid acid catalyst, removing moisture by using anhydrous magnesium sulfate, distilling to remove residual butanol, distilling under reduced pressure, collecting 180-190 ℃/1.33kPa (10) or 200-210 ℃/2.67kPa (20 kPa) fraction to obtain dibutyl phthalate, the yield was 97%.
By adopting the method, ZrPDPP with other molar ratios can be used; the MPDPP can be used as the catalyst by the same method, and the yield of the MPDPP can reach more than 95 percent.
[ example 7 ]: MPDPP is used as a solid acid catalyst for preparing biodiesel, ZrPDPP (0.78) is used as a catalyst to catalyze transesterification reaction in the preparation process of the biodiesel, and cottonseed oil and methanol are used as raw materials: 5g of cottonseed oil is weighed and added into 100mL of methanol, 0.2g of ZrPDPP (0.78) is added, and heating, stirring and refluxing are carried out for 12h, so that the yield of the fatty acid methyl ester reaches 94%.
The MPDPP used as the solid acid catalyst for the catalytic reaction of the biodiesel can be carried out by the same method, and the yield of the fatty acid methyl ester is higher than 93 percent.
[ example 8 ]: ZrPDPP (0.78) is used as a proton conductor for preparing a high-temperature proton exchange membrane.
(1) Preparation of polybenzimidazole containing pyrazine group (PzPBI): the compound is prepared by reacting 2, 6-pyrazinedicarboxylic acid with 3, 3' -diaminobenzidine (DABz), and comprises the following specific reaction steps: polyphosphoric Acid (PPA) (100g) was added to a three-necked flask equipped with electric stirring and nitrogen blanketing, and stirred at 160 ℃ for 1h under nitrogen blanket to remove excess water and air. DABz (4.00g,18.7mmol) and 2, 6-pyrazinedicarboxylic acid (3.14g,18.7mmol) were mixed well and slowly added to a three-necked flask. And controlling the nitrogen flow rate to prevent DABz from being oxidized, raising the reaction temperature to 200 ℃, and continuously preserving heat and stirring for reaction for 5-8 hours. The polymerization system gradually became viscous with increasing reaction time. Stopping reaction when the viscosity is proper, slowly transferring the reaction mixed solution into a large amount of deionized water for spinning, cleaning, drying, crushing, washing with deionized water for multiple times to remove polyphosphoric acid and unreacted reactants to obtain PzPBI, and measuring the molecular weight of the PzPBI by using a Ubbelohde viscometer. The viscosity average molecular weight is 4.5 to 5.5 ten thousand.
(2) Other PBI with pyrazine group are prepared by the following steps: the same method as (1) only needs to change 2, 6-pyrazine dicarboxylic acid into 2, 5-pyrazine dicarboxylic acid or 2, 3-pyrazine dicarboxylic acid, other operations are the same as (1), so that PzPBI containing different pyridine groups can be obtained, and products are respectively recorded as: 3,5-PzPBI or 2, 3-PzPBI.
(3) Preparation of a composite proton exchange membrane doped with zrPDPP (0.78) to polybenzimidazole (PzPBI): for example, ZrPDPP (0.78) is doped 40%. 1.0g of PzPBI was added to 10ml of N, N' -dimethylacetamide (DMAc), and the mixture was magnetically stirred at 80 ℃ for 24 hours to dissolve it sufficiently, and insoluble materials were removed by suction filtration. At 50.05g of TGIC as a crosslinking agent was added to the filtrate at 0 ℃ and the mixture was stirred for 2.5 hours to dissolve it sufficiently. Then 0.70g of ZrPDPP (0.78) is added, and the mixture is stirred for 3 hours to be fully dispersed in the casting solution. The bubbles were removed by ultrasonic oscillation for 1h, then cast on a glass plate, cast at 60 ℃ for 12h, heated at 120 ℃ for 12h to remove the solvent, and then heated at 160 ℃ for 6h to fully crosslink the PBI and TGIC. The obtained film was 0.1mol L-1H2SO4Soaking the membrane in the water solution for 24h at room temperature to fully acidify the doped membrane, and then soaking the membrane in deionized water for 24h (changing water every 6 h) to wash away sulfuric acid in the membrane to obtain the PzPBI-TGIC (5%)/ZrPDPP (0.78) (40%) composite membrane.
(4) Other PBI preparation methods are the same as the (1) part in example 8. Except that 2, 6-pyrazinedicarboxylic acid is changed to another dicarboxylic acid (e.g., isophthalic acid, 2, 6-pyridinedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 1, 5-imidazoledicarboxylic acid, 4' -biphenyldicarboxylic acid, etc.)
(5) The preparation method of the PBI composite membrane crosslinked by other crosslinking agents and doped with other ZrPDPP (0.78) is the same as the part of experiment (3) in example 8, except that the crosslinking agent TGIC is changed into other crosslinking agents, and the dosage of the ZrPDPP (0.78) is changed into other amounts from 0.7 g. The test results of the composite films are shown in Table 5.
[ example 9 ]: assembling the high-temperature proton exchange membrane fuel cell and testing the cell performance. According to the single cell assembly method, the prepared membrane electrode is assembled into a single cell and connected to a fuel cell test system for testing, the anode uses hydrogen with the relative humidity of 50% as fuel, the flow rate is 40mL/min, the working temperature of the cell is 150 ℃, the oxygen flow rate of the cathode is 20mL/min, and the back pressure is 0.2 MPa. The cell performance was tested by first activating and then testing the performance, and the results of testing the MEA for the different membranes are shown in table 6.
[ example 10 ]: the same method as in example 4 is adopted, zirconium oxychloride is replaced by ceric ammonium nitrate, ferric trichloride, yttrium nitrate or lanthanum nitrate respectively, and zirconium salt, iron salt, yttrium salt or lanthanum salt with different ratios can be obtained according to different molar ratios. The properties of these salts were investigated using the methods of example 5, example 6, example 7, example 8 and example 9, respectively, and the preparation processes and properties are shown in tables 3, 4, 5 and 6.
TABLE 3 comparison of preparation process conditions and performances of MPDPP proton conductor
Figure GDA0003130899980000101
Note: unit of IEC is meq.g-1。
TABLE 4 proton conductivity (S/cm) of MPDPP proton conductor at 180 deg.C under different properties and low humidity
Figure GDA0003130899980000102
TABLE 5 proton conductivity (S/cm) of composite membranes prepared by doping MPDPP to PBI
Figure GDA0003130899980000111
Note: 2, 6-PzPBI: novel PBI obtained by condensing 2, 6-pyrazinedicarboxylic acid and 3, 3' -diaminobenzidine
2, 5-TpPBI: novel PBI obtained by condensing 2, 5-thiophenedicarboxylic acid and 3, 3' -diaminobenzidine
2, 6-PyPBI: novel PBI obtained by condensing 2, 6-pyridinedicarboxylic acid and 3, 3' -diaminobenzidine
The abbreviation of the crosslinking agent with multiple functionality and Chinese full name:
TGIC: 1,3, 5-tris (oxiran-2-ylmethyl) -1,3, 5-triazine-2, 4, 6-trione
TGDDM: n, N, N ', N ' -Tetraepoxypropyl-4, 4 ' -diaminodiphenylmethane
CMPSU: chloromethylated polyether sulfone
CMPBI: chloromethylated polybenzimidazole
PDCP: polydichlorophosphazene
TABLE 6 Performance testing of Membrane electrodes prepared from MPDPP-doped PBI composite membranes
Figure GDA0003130899980000121
Note: 2, 6-PzPBI: novel PBI obtained by condensing 2, 6-pyrazinedicarboxylic acid and 3, 3' -diaminobenzidine
2, 6-PyPBI: novel PBI obtained by condensing 2, 6-pyridinedicarboxylic acid and 3, 3' -diaminobenzidine
2, 3-PzPBI: novel PBI obtained by condensing 2, 3-pyrazinedicarboxylic acid and 3, 3' -diaminobenzidine
The abbreviation of the crosslinking agent with multiple functionality and Chinese full name:
TGIC: 1,3, 5-tris (oxiran-2-ylmethyl) -1,3, 5-triazine-2, 4, 6-trione
TGDDM: n, N, N ', N ' -Tetraepoxypropyl-4, 4 ' -diaminodiphenylmethane
CMPSU: chloromethylated polyether sulfone
PDCP: polydichlorophosphazene.

Claims (5)

1. The preparation method of the poly (diphosphonate phosphazene) high-temperature proton conductor is characterized by comprising the following steps of: heating and ring-opening polymerizing hexachlorocyclotriphosphazene serving as a raw material in a high-boiling-point solvent to obtain poly (dichlorophosphazene), and reacting the poly (dichlorophosphazene) with phosphite triester to obtain poly (bis (dialkoxy phosphate) phosphazene); hydrolyzing poly (bis (dialkoxyphosphate) phosphazene) in concentrated hydrochloric acid to obtain poly (diphosphophosphazene), and polymerizing the poly (diphosphophosphazene) with one or more of high valence metal ions to obtain water-insoluble poly (diphosphophosphazene): polymerizing under ring opening at 210-250 ℃ to obtain poly (dichlorophosphazene); reacting poly (dichlorophosphazene) with phosphite triester at 100-120 ℃ to obtain poly (bis (dialkoxy phosphate) phosphazene); hydrolyzing poly (bis (dialkoxy phosphate) phosphazene) concentrated hydrochloric acid to obtain poly (diphosphonithosphazene); reacting poly (diphosphophosphazene) with a high-valence metal ion solution to obtain poly (diphosphophosphazene) with different proportions; poly (diphosphophosphazene) as organic-inorganic composite temperature-resistant proton conductor for solid acid catalyst, proton conductor, proton exchange membrane additive, sensor and fuel cell membrane electrodeA sub-conductive material; the high boiling point solvent is characterized in that: a solvent having a boiling point greater than 220 ℃ and stable to hexachlorocyclotriphosphazene and poly (dichlorophosphazene); the high-valence metal ions are selected from: zr4+、Ce4+、Fe3+、Co3+、La3+Or Y3+One or more of (a).
2. The method for preparing a poly (diphosphophosphazene) high temperature proton conductor according to claim 1, wherein the high boiling point solvent is selected from the following solvents: aromatic solvent oil, diphenyl ether, sulfolane, glyceryl triacetate, pentaerythritol tetraacetate, polyethylene glycol diacetate, liquid paraffin and one or more of methyl naphthalene oil.
3. The method of preparing a poly (diphosphophosphazene) high temperature proton conductor of claim 1, wherein: the phosphite triester selects alcohol generated by hydrolysis reaction, has low boiling point and is easy to be evaporated and removed, and the phosphite triester selects the following components: one or a mixture of more of trimethyl phosphite, triethyl phosphite, tripropyl phosphite or triisopropyl phosphite.
4. The method of preparing a poly (diphosphophosphazene) high temperature proton conductor of claim 1, wherein: the salt of high valence metal ion is soluble in water, and can ionize metal ion in solution, and one or more of acetate, hydrochloride and nitrate are selected.
5. The method for preparing a poly (diphosphophosphazene) high-temperature proton conductor according to claim 1, wherein the mass ratio of the high-valence metal ions to the poly (diphosphophosphazene) is 2: 5-3: 2.
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