CN115991835B - Wide-temperature-zone polymerized phosphonic acid resin and preparation method thereof - Google Patents

Wide-temperature-zone polymerized phosphonic acid resin and preparation method thereof Download PDF

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CN115991835B
CN115991835B CN202211276230.1A CN202211276230A CN115991835B CN 115991835 B CN115991835 B CN 115991835B CN 202211276230 A CN202211276230 A CN 202211276230A CN 115991835 B CN115991835 B CN 115991835B
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phosphonic acid
integer
monomer
reaction
acid resin
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CN115991835A (en
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张永明
张恒
王振华
丁涵
张建宏
张烁烁
刘烽
邹业成
许胜杰
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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    • Y02E60/50—Fuel cells

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Abstract

The invention belongs to the field of fluorine-containing high polymer materials, and particularly relates to a wide-temperature-zone polymerized phosphonic acid resin and a preparation method thereof. The polymeric phosphonic acid resin is composed of fluorine-containing olefin units, perfluorovinyl ether phosphonic acid units, perfluorovinyl phosphonic acid units and perfluorovinyl ether sulfonic acid units. The invention also discloses a preparation method of the polymeric phosphonic acid resin. The polymeric phosphonic acid resin has the advantages of high ion exchange capacity, high chemical medium tolerance, high mechanical strength, high dimensional stability, low membrane resistance, long service life and the like, has high proton conductivity in a wider temperature range, and can overcome the problem of reduced high-temperature proton conductivity of the traditional perfluorinated ion exchange resin. The polymeric phosphonic acid resin can be used in the fields of fuel cells, electrolytic systems and catalytic layers.

Description

Wide-temperature-zone polymerized phosphonic acid resin and preparation method thereof
Technical Field
The invention belongs to the field of fluorine-containing high polymer materials, relates to a polymeric phosphonic acid resin and a preparation method thereof, and particularly relates to a polymeric phosphonic acid resin with a wide temperature range and a preparation method thereof.
Background
A fuel cell is a power generation device that directly converts chemical energy of fuel and oxidant into electric energy through an electrochemical reaction. Mainly comprises a positive electrode, a negative electrode, electrolyte and auxiliary equipment. Because the fuel cell has the advantages of high efficiency, quick start, small pollution and the like, the fuel cell is considered as a fourth power generation technology which hopefully provides a large amount of electric energy after wind power, water power and solar energy, is a green energy technology, can effectively relieve two major problems of 'energy shortage' and 'environmental pollution' facing the world at present, and realizes the diversification of energy. Besides the general characteristics of fuel cells, proton Exchange Membrane Fuel Cells (PEMFCs) have the characteristics of quick start, no electrolyte loss, no corrosion, high energy conversion rate, long service life, light weight, small volume, no pollution, infrared radiation and the like, and have wide application prospects in the fields of traffic power sources, portable power sources and fixed power station power sources.
In the fuel cell, the proton exchange membrane provides a channel for migration and transportation of protons, so that the protons pass through the membrane to reach the cathode from the anode to form a loop with the electron transfer of an external circuit, and current is provided to the outside, therefore, the performance of the proton exchange membrane plays a very important role in the performance of the fuel cell, and the service life of the fuel cell is directly influenced by the quality of the proton exchange membrane. The Proton Exchange Membrane (PEMFC) most commonly used so far is still a Nafion membrane from dupont in the united states, which is a perfluorosulfonic acid membrane that has high temperature and water content requirements, and the Nafion series membranes have an optimum operating temperature of 70-90 ℃ beyond which the water content is drastically reduced and the conductivity is rapidly reduced, preventing the problems of increasing the electrode reaction rate and overcoming catalyst poisoning by properly increasing the operating temperature. Therefore, development of a proton exchange resin having high conductivity under high temperature conditions is desired.
Development of proton exchange resins with high proton conductivity under high temperature conditions is currently mainly focused on phosphoric acid doped aromatic heterocyclic polymer proton membranes, for example, chinese patent CN112375211a provides a polyaromatic hydrocarbon material containing imidazole groups, and a great amount of aromatic and aromatic heterocyclic structures are doped in the polyaromatic hydrocarbon material. The membrane has the advantages of simple preparation process, strong high-temperature proton conductivity, low-temperature working efficiency, incapability of being started quickly, poor stability, short service life and the like. The phosphoric acid doped proton membrane is degraded due to the attack of free radicals (OH or OOH) generated in the working environment, and the proton conduction of the phosphoric acid doped proton membrane is difficult at the temperature below 100 ℃, so that the mechanical property and the proton conduction property of the proton membrane are seriously reduced. Therefore, the current phosphoric acid doped polymer proton membrane cannot meet the actual use requirement of the fuel cell under the low temperature condition, and the stable operation of the polymer proton membrane in a wider temperature area cannot be realized.
Disclosure of Invention
In order to solve the problems of the prior art that the perfluorinated sulfonic acid resin has low proton conductivity under the high temperature condition and the phosphonic acid doped perfluorinated sulfonic acid resin cannot stably run under the low temperature condition, the invention prepares a polymeric phosphonic acid resin by the multi-element copolymerization of fluoroolefins, perfluorinated vinyl ether phosphonate, perfluorinated vinyl phosphonate and perfluorinated sulfonyl fluoride vinyl ether monomers, and satisfies the high exchange capacity perfluorinated ion polymer with high conductivity and good thermal stability in a wide temperature area and a preparation method thereof. On the other hand, the copolymer structure of the perfluorinated ion polymer is introduced with a perfluorinated vinyl phosphonate structural unit with a side chain free of C-O bonds, so that the rigidity of the perfluorinated ion polymer molecular chain is improved, and the heat resistance and the high-temperature heat stability of the perfluorinated ion polymer can be improved.
The above object of the present invention is achieved by the following technical scheme:
the polymeric phosphonic acid resin with wide temperature range consists of fluorine-containing olefin units, perfluorovinyl ether phosphonic acid units, perfluorovinyl phosphoric acid units and perfluorovinyl ether sulfonic acid units, and has the structural formula:
wherein k is an integer of 0 to 3, f is an integer of 1 to 4, preferably k=0 to 1, f=2; g is an integer from 0 to 4, preferably g=2; t is an integer from 0 to 3, v is an integer from 1 to 4, preferably t=0-1, v=2; a. b and c are integers from 1 to 20, a ', b ' and c ' are integers from 1 to 3; wherein R is- (OCF) 2 ) m (CF 2 ) n X, X is Cl orF, performing the process; m and n are integers from 0 to 3; x, y, z satisfy the following conditions: x/(x+y+z) =0.1 to 0.5, y/(x+y+z) =0.1 to 0.5, and z/(x+y+z) =0.1 to 0.6.
The wide-temperature-zone polymerized phosphonic acid resin is obtained by a transformation reaction of a polymerized phosphonic acid precursor polymer formed by copolymerization of a fluorine-containing olefin monomer, a perfluorovinyl ether phosphonate monomer, a perfluorovinyl phosphonate monomer and a perfluorosulfonyl fluoride vinyl ether monomer.
Further, the structural formula of the repeating unit of the polymerized phosphonic acid precursor polymer is as follows:
wherein k is an integer of 0 to 3, f is an integer of 1 to 4, preferably k=0 to 1, f=2; g is an integer from 0 to 4, preferably g=2; t is an integer from 0 to 3, v is an integer from 1 to 4, preferably t=0-1, v=2; a. b and c are integers from 1 to 20, a ', b ' and c ' are integers from 1 to 3; r is- (OCF) 2 ) m (CF 2 ) n X and X are Cl or F, m and n are integers of 0-3; the molar ratio of x, y and z satisfies the following conditions: x/(x+y+z) =0.1-0.5, y/(x+y+z) =0.1-0.5, z/(x+y+z) =0.1-0.6, p is an integer of 1-6, preferably p=1-3; q is an integer from 1 to 6, preferably q=1 to 3.
The structural formula of the perfluorovinyl ether phosphonate monomer is as follows:
wherein k=an integer of 0-3, preferably k=0-1; f=an integer of 1 to 4, preferably f=2; p=an integer of 1 to 6, preferably p=1 to 3.
The structural formula of the perfluorovinyl phosphonate monomer is as follows:
wherein g=an integer of 0-4, preferably g=0-2; q=an integer of 1 to 6, preferably q=1 to 3.
The structural formula of the perfluorosulfonyl fluoride vinyl ether monomer is as follows:
wherein t=an integer from 0 to 3, preferably t=0 to 1; v=an integer of 1-4, preferably v=2.
The mole percentage of each polymerized unit in the polymerized phosphoric acid precursor copolymer is as follows: the fluorine-containing olefin polymerization unit accounts for 50-85% of the total mole fraction, the perfluorovinyl ether phosphonate polymerization unit accounts for 2-25% of the total mole fraction, the perfluorovinyl phosphonate polymerization unit accounts for 2-25% of the total mole fraction, and the perfluorosulfonyl fluoride vinyl ether polymerization unit accounts for 1-25% of the total mole fraction.
Preferably, the molar content percentage of each polymerization unit in the polymerized phosphonic acid precursor copolymer is as follows: the fluorine-containing olefin polymerization unit accounts for 60-85% of the total mole fraction, the perfluorovinyl ether phosphonate polymerization unit accounts for 5-20% of the total mole fraction, the perfluorovinyl phosphonate polymerization unit accounts for 5-20% of the total mole fraction, and the perfluorosulfonyl fluoride vinyl ether polymerization unit accounts for 5-20% of the total mole fraction.
The number average molecular weight of the polymeric phosphonic acid polymer is 10 to 60 ten thousand, preferably 15 to 50 ten thousand, more preferably 20 to 40 ten thousand. The molecular weight distribution index (weight average molecular weight to number average molecular weight) of the above perfluorinated ion polymer is 1.0 to 2.0, preferably 1.2 to 1.6.
The invention also provides a preparation method of the polymerized phosphonic acid resin, which comprises the following specific steps:
s1: carrying out copolymerization reaction on fluorine-containing olefin, perfluoro vinyl ether phosphonate monomer, perfluoro vinyl phosphonate monomer and perfluoro sulfonyl fluoride vinyl ether monomer under the action of an initiator to obtain a polymerized phosphonic acid precursor polymer;
s2: and soaking the prepared polymerized phosphonic acid precursor polymer in alkali liquor for transformation reaction, filtering after the transformation reaction is finished, pickling, and washing with water to obtain the polymerized phosphonic acid resin.
In step S1, the copolymerization reaction includes a step of performing solution polymerization in a fluorine-containing solvent or a step of performing emulsion polymerization in an aqueous phase or a step of performing suspension polymerization in an aqueous phase.
Preferably, the copolymerization is an emulsion polymerization or a suspension polymerization in an aqueous phase.
In solution polymerization, the fluorine-containing solvent is a solvent or solvents or any combination thereof that is/are a fluorinated liquid compound or oligomer containing no chlorine atoms; preferably, the fluorine-containing solvent is a fluorocarbon solvent; more preferably, the fluorine-containing solvent is CFC-113a.
The specific steps of emulsion or suspension polymerization in the aqueous phase include:
1) Adding pure water, perfluorovinyl ether phosphonate monomer, perfluorovinyl phosphonate monomer, perfluorosulfonyl fluoride vinyl ether monomer, emulsifier/dispersant into a reaction kettle;
2) Filling fluoroolefin into the reaction kettle through the gas metering tank until the pressure is 0.01-10MPa, preferably 0.2-5MPa, more preferably 0.2-2MPa;
3) Heating the reaction kettle to 0-100 ℃, adding an initiator into the reaction system through a metering pump to initiate reaction, continuously adding fluoroolefin monomer and the initiator into the reaction kettle, keeping the reaction kettle at the reaction pressure, and reacting for 0.5-48 hours, preferably 0.5-24 hours, more preferably 0.5-8 hours;
4) Stopping adding the initiator and the fluorine-containing olefin monomer into the reaction kettle when the reaction is finished, and emptying and recovering the unreacted fluorine-containing olefin monomer through a reaction kettle emptying pipeline and a recovery tank; and (3) obtaining milky polymer slurry, feeding the liquid slurry into post-treatment equipment through an emptying system, shearing at high speed or otherwise, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the polymerized phosphonic acid precursor polymer. The perfluorovinyl ether phosphonate monomer, perfluorovinyl phosphonate and perfluorosulfonyl fluoride monomer in the filtrate are recycled by a recycling system.
Wherein the initiator is selected from the group consisting of peroxides, perfluoroalkyl peroxides, N 2 F 2 One or more of azo compounds or persulfates and redox systems.
Preferably, the initiator is selected from, but not limited to, perfluorobutyryl peroxide, perfluoropropoxypropyl peroxide, persulfates,-SO 2 F-perfluoro-2, 5, 8-trimethyl-3, 6, 9-trioxa-undecyl peroxide, N 2 F 2 One or more of the following.
The addition amount of the initiator is 0.01-5%.
Wherein, in the step 1), an emulsifier is selected when the reaction is emulsion polymerization; dispersing agent is selected when the reaction is suspension polymerization.
The emulsifier allows for better dispersion of the perfluorophosphonate monomer and perfluorosulfonyl fluoride vinyl ether monomer in the aqueous phase during the emulsion polymerization step. The emulsifier is selected from one or any combination of anionic emulsifier, nonionic emulsifier or reactive emulsifier.
Preferably, the emulsifier is selected from one or more of sodium dodecyl sulfonate, polyoxyethylene nonylphenol ether, and potassium perfluorovinyl ether sulfonate.
In the emulsion polymerization step, the mass percentage concentration of the emulsifier in water is 0.01-40%, preferably 0.1-20%, the mass percentage concentration of the perfluorovinyl ether phosphonate monomer in water is 5-60%, preferably 5-50%, the mass percentage concentration of the perfluorovinyl phosphate monomer in water is 5-60%, preferably 5-50%, and the mass percentage concentration of the perfluorosulfonyl fluoride vinyl ether monomer in water is 1-60%, preferably 5-50%, based on the total weight of the water phase. In the emulsion polymerization, the fluoroolefin monomer is introduced into the reaction system in the form of a gas.
In the suspension polymerization step, the dispersant is selected from one or any combination of inorganic salt powder or organic polymer.
Preferably, the dispersant is selected from one or more of, but not limited to, limestone, calcium carbonate, methylcellulose.
Preferably, in the suspension polymerization step, the concentration of the dispersant in water is 0.01 to 40% by mass, preferably 0.1 to 20% by mass, the concentration of the perfluorovinyl ether phosphonate monomer in water is 5 to 60% by mass, preferably 5 to 50% by mass, the concentration of the perfluorovinyl phosphate monomer in water is 5 to 60% by mass, preferably 5 to 50% by mass, and the concentration of the perfluorosulfonyl fluoride vinyl ether monomer in water is 1 to 60% by mass, preferably 5 to 50% by mass.
In step S2, the polymerized phosphonic acid precursor polymer is converted into a salt form or an acid form by a conversion reaction, and has an ion exchange function.
In the step S2, the mass ratio of the polymerized phosphonic acid precursor polymer to the alkali liquor is 1 (1-10); the alkali liquor is sodium hydroxide, potassium hydroxide solution or lithium hydroxide, ammonia water, sodium carbonate, potassium carbonate or lithium carbonate, and the concentration is 0.01-35%, preferably 0.1-25%. The reaction time for the transformation is 1-144 hours, preferably 5-72 hours, the transformation temperature is 20-150 ℃, preferably 20-100 ℃.
The acid washing solution is common protonic acid or mixed solution of protonic acid such as nitric acid, sulfuric acid, hydrochloric acid, and the like, and the concentration is 1-30%, preferably 5-20%. The pickling time is 1-144 hours, preferably 5-72 hours, and the pickling temperature is 20-150 ℃, preferably 20-100 ℃.
The polymeric phosphonic acid resin can be used in the fields of manufacturing fuel cells, electrolytic systems, fuel cell catalyst layers and the like.
The invention provides a polymeric phosphonic acid resin dispersion liquid, which comprises polymeric phosphonic acid resin and an organic solvent.
The organic solvent is one or more of N-propanol, isopropanol, methanol, acetone, N-Dimethylformamide (DMF), methylamide, acetaldehyde, ethylene glycol and cyclohexanone.
In the polymerized phosphonic acid resin dispersion liquid, the mass percent of the polymerized phosphonic acid resin is 2.5-50 wt%, the mass percent of the pure water is 10-95 wt%, and the mass percent of the organic solvent is 2.5-87.5 wt%;
preferably, in the polymerized phosphonic acid resin dispersion liquid, the mass percent of the polymerized phosphonic acid resin is 5-40 wt%, the mass percent of the pure water is 15-75 wt%, and the mass percent of the organic solvent is 5-75 wt%.
The invention also provides a preparation method of the polymerized phosphonic acid resin dispersion liquid, which comprises the following specific operation steps:
s1: adding the polymeric phosphonic acid resin, pure water and an organic solvent into an autoclave;
s2: mechanically stirring under the protection of inert gas, dissolving at high temperature, stopping heating, stirring, and cooling to room temperature to obtain mixed solution of polymerized phosphonic acid resin, pure water and ether generated by decarboxylation of organic solvent;
S3: and (3) separating the mixed solvent obtained in the step (S2) from liquid to obtain the polymerized phosphonic acid resin dispersion liquid.
In step S2, the inert gas is selected from one of nitrogen, argon or xenon.
The temperature of the mechanical stirring is 120-280 ℃;
preferably, the temperature of the mechanical stirring is 140-260 ℃.
The stirring pressure is 1MPa-5MPa.
Preferably, the stirring pressure is 2MPa to 4MPa.
The mechanical stirring time is 2-20 h;
preferably, the mechanical stirring time is 4-15 h.
In step S3, the liquid-liquid separation method includes distillation and extraction separation.
Preferably, the extraction and separation method comprises the following steps: transferring the mixed solution into a separating funnel, extracting and separating the mixed solution by carbon tetrachloride at normal temperature and normal pressure, and taking the lower layer solution to obtain the polymerized phosphonic acid resin dispersion liquid.
The micelle particle size of the polymerized phosphonic acid resin dispersion liquid is 100-400nm;
the polymeric phosphoric acid resin solution of the invention can be used in the fields of manufacturing fuel cells, electrolytic systems, fuel cell catalyst layers and the like.
Compared with the prior art, the invention has at least the following advantages:
1. the polymerization type phosphonic acid resin provided by the invention solves the problem of poor thermal stability of the prior phosphoric acid doped perfluorinated ion polymer and the problem of low high-temperature conductivity of the perfluorinated ion polymer by the synergistic effect of the perfluorinated vinyl ether phosphonic acid polymerization unit, the perfluorinated vinyl phosphoric acid polymerization unit and the perfluorinated vinyl ether sulfonic acid polymerization unit, realizes that the polymerization type phosphonic acid resin has high conductivity in the temperature region below the freezing point and above the boiling point, and effectively widens the temperature range of the prior perfluorinated sulfonic acid resin used in the field of fuel cell membranes.
2. The copolymer structure of the perfluorinated ion polymer adopts the perfluorinated vinyl ether phosphonate unit with the side chain containing a C-O bond and the perfluorinated vinyl phosphonate unit without the side chain containing a C-O bond, the C-O bond can be broken and degraded under the high temperature condition, and the polymerization unit with the full C-C bond is introduced into the side chain, so that the high-temperature thermal stability of the whole perfluorinated ion polymer can be improved.
3. The polymerized phosphoric acid resin dispersion liquid of the invention is uniformly dispersed, and can be prepared into a perfluorinated proton exchange membrane with two proton exchange groups of sulfonic acid and phosphoric acid, so that the perfluorinated proton exchange membrane has very high ion exchange capacity, has various chemical medium resistance, high conductivity and proton conductivity, and is very suitable for being used in a high-temperature fuel cell or a fuel cell catalyst layer.
Drawings
FIG. 1 is a GPC data diagram of polymeric phosphonic acid precursor polymers of example 1;
FIG. 2 is a GPC data diagram of the polymerized phosphonic acid precursor polymer of example 2;
FIG. 3 is a graph of infrared data for the polymerized phosphonic acid precursor polymer of example 1;
FIG. 4 is a graph of infrared data for the polymerized phosphonic acid precursor polymer of example 2.
Detailed Description
The following examples are further illustrative of the invention, which is not limited thereto. The reaction kettles used in the examples were all 10L stainless steel high-pressure reaction kettles, equipped with temperature sensors, pressure sensors, heating circulation systems, cooling circulation systems, stirring motors, internal cooling water pipes, liquid metering pumps, gas feed valves, liquid feed valves, and material discharge valves in the reaction kettles, unless otherwise specified.
The ion exchange capacity is the result of the measurement of conversion of sulfonyl fluoride to sulfonic acid and conversion of phosphonate to phosphorous acid unless otherwise specified in the examples below.
The embodiment is not specifically described, and the percentage content is mass percentage.
The perfluoroalkyl initiators used in the synthesis of the present invention can be prepared according to techniques known in the art, the preparation methods recommended in the present invention are described in j. Org. Chem.,1982, 47 (11): 2009-2013.
Ammonium persulfate adopted in the synthesis process is purchased from a national drug group; n (N) 2 F 2 Gases were purchased from the east Yue chemical Co.
Tetrafluoroethylene adopted in the polymerization process is purchased from Shandong Dongyue polymer material limited company; perfluoro vinyl ether phosphonate monomers can be prepared using the methods disclosed in literature Novel phosphonated perfluorocarbon polymers [ J ], masaaki Yamabe et al, european Polymer Journal (2000) 1035-1041, CN 200910230218.5; perfluoro vinyl phosphonate monomers can be prepared using the methods disclosed in literature Facile Synthesis of Fluorinated Phosphonates Via Photochemical and Thermal Reactions [ J ], haridasan K.Nair and Donald J.Burton, J.Am.Chem.Soc.1997,119,9137-9143; the perfluorosulfonyl fluoride vinyl ether monomer adopts the patent application number as follows: CN200910229444.1, CN200910229446.0, CN200910230218.5, CN 201810798170.7.
Example 1:
cleaning the reaction kettle, adding 5000g of CFC-113a fluorine-containing organic solvent, starting a stirring device, vacuumizing, filling high-purity nitrogen for three times for replacement, testing the oxygen content in the reaction kettle to be less than 1ppm, vacuumizing, and adding 900g of perfluorovinyl ether phosphonate monomer (CF) into the reaction kettle through a liquid feed valve 2 ＝CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -P＝O-(OCH 2 CH 3 ) 2 ) 275g of perfluorovinyl phosphonate monomer (CF) 2 ＝CF-CF 2 -P＝O-(OCH 2 CH 3 ) 2 ) 325g of perfluorovinyl ether sulfonyl fluoride monomer (CF) 2 ＝CF-O-CF 2 CF 2 -SO 2 F) Then, tetrafluoroethylene monomer was charged into the autoclave to a pressure of 0.5MPa, the temperature was raised to 30℃and 3.5g of perfluorobutyryl peroxide (CF) was added by a metering pump 3 CF 2 CF 2 CO-OO-COCF 2 CF 2 CF 3 ) The polymerization was initiated and tetrafluoroethylene (CF) 2 ＝CF 2 ) The monomer keeps the reaction pressure at 0.5MPa, 0.85g of initiator is added into the system every 15min, after 2h of reaction, the initiator is stopped to be added, and after the reaction is continued for 15min, the monomer of tetrafluoroethylene is stopped to be added. Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing feed liquid in the kettle into a post-treatment system through a discharging valve, settling and flocculating by adding chloroform solvent to separate out polymer, and drying in a 100 ℃ oven to obtain the polymerized phosphonic acid precursor polymer. The chloroform, 113a fluorine-containing organic solvent, unreacted perfluorophosphate ester monomer and perfluorosulfonyl fluoride vinyl ether monomer are recycled after being recovered by a recovery system.
Polymer data: warp F 19 NMR and IR analyses showed that the copolymer was a tetrapolymer, and the polymer structure was found to have 58.18% by mole of polymerized units of tetrafluoroethylene, 24.60% by mole of polymerized units of perfluorovinyl ether phosphonate, 8.12% by mole of polymerized units of perfluorovinyl phosphonate, 9.10% by mole of polymerized units of perfluorosulfonyl fluoride, and total ion exchange resinThe capacity is: 1.25mmol/g dry resin.
GPC measured molecular weight was 23.4 million, and molecular weight distribution number 1.65.
IR spectrogram: 1468cm -1 Is the s=o vibration absorption peak in sulfonyl fluoride; 1294cm -1 A vibration absorption peak for p=o in phosphonate; 1030cm -1 Absorption peaks for C-O-C bonds 1230 and 1155cm -1 The two strongest absorptions are caused by CF vibration; 720cm -1 、640cm -1 from-CF after tetrafluoroethylene copolymerization 2 -CF 2 Vibration absorption causes.
Example 2:
cleaning the reaction kettle, adding 5.0L deionized water and 200g sodium dodecyl benzene sulfonate, starting a stirring device, vacuumizing, filling high-purity nitrogen for three times, testing that the oxygen content in the reaction kettle is below 1ppm, vacuumizing, and adding 850g perfluorovinyl ether phosphate monomer (CF) into the reaction kettle through a liquid feed valve 2 ＝CF-O-(CF 2 )-P＝O-(OCH 3 ) 2 ) 850g of perfluorovinyl phosphoric acid monomer (CF) 2 ＝CF-CF 2 -P＝O-(OC 3 H 7 ) 2 ) 200g of perfluorovinyl ether sulfonyl fluoride monomer (CF) 2 ＝CF-O-CF 2 CF(CF 3 )-(CF 2 ) 2 -SO 2 F) Then, tetrafluoroethylene monomer was charged into the reaction vessel to a pressure of 0.9MPa, the temperature was raised to 40℃and 10g of perfluoropropoxypropyl peroxide (CF) was added by a metering pump 3 CF 2 CF 2 OCF(CF 3 )CO-OO-COCF(CF 3 )OCF 2 CF 2 CF 3 ) Initiating polymerization reaction, continuously introducing tetrafluoroethylene monomer, keeping the reaction pressure at 0.9MPa, adding 2.0g of initiator into the system every 20min, stopping adding the initiator after 2.5h of reaction, and stopping adding the tetrafluoroethylene monomer after the reaction is continued for 20 min. Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing milky white slurry in the kettle into a post-treatment system through a discharging valve, performing high-speed shearing, demulsification and condensation, filtering and separation to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the polymerized phosphonic acid precursor polymer. Passing throughThe perfluorophosphate monomer and perfluorosulfonyl fluoride vinyl ether monomer in the filtrate are recycled after being recovered by a recovery system.
Polymer data: warp F 19 NMR and IR analyses showed that the copolymer had a fluorinated nuclear magnetic resonance value of 65.28% by mole of polymerized units of tetrafluoroethylene, 13.21% by mole of polymerized units of perfluorovinyl ether phosphonate, 16.31% by mole of polymerized units of perfluorovinyl phosphonate, 5.20% by mole of polymerized units of perfluorosulfonyl fluoride, and the total ion exchange capacity of the resin was: 1.53mmol/g dry resin.
GPC measured molecular weight was 30.9 ten thousand, and molecular weight distribution number 1.63.
IR spectrogram: 1468cm -1 Is the s=o vibration absorption peak in sulfonyl fluoride; 1296cm -1 A vibration absorption peak for p=o in phosphonate; 1028cm -1 Absorption peak of C-O-C bond, 984cm -1 is-CF 3 Vibration-induced; 1228 and 1148cm -1 The two strongest absorptions are caused by-C-F vibrations; 720cm -1 、641cm -1 from-CF after tetrafluoroethylene copolymerization 2 -CF 2 Vibration absorption causes.
Example 3:
cleaning the reaction kettle, adding 5.0L deionized water, 125g sodium dodecyl benzene sulfonate and 80g nonylphenol polyoxyethylene ether NP-10 emulsifier, starting a stirring device, vacuumizing, filling high-purity nitrogen for three times, testing the oxygen content in the reaction kettle to be less than 1ppm, vacuumizing, and adding 375g of perfluorovinyl ether phosphonate monomer (CF) into the reaction kettle through a liquid feed valve 2 ＝CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -P＝O-(OCH 3 ) 2 ) 250g of perfluorovinyl phosphonate monomer (CF) 2 ＝CF-CF 2 CF 2 -P＝O-(OCH 3 ) 2 ) 1050g of perfluorovinyl ether sulfonyl fluoride monomer (CF) 2 ＝CF-O-CF 2 CF 2 -SO 2 F) Then, tetrafluoroethylene monomer is filled into a reaction kettle until the pressure is 3.5MPa, the temperature is raised to 80 ℃, 350g of 10% ammonium persulfate aqueous solution is added by a metering pump to initiate polymerization reaction, and the polymerization reaction is maintainedContinuously introducing tetrafluoroethylene monomer, keeping the reaction pressure at 3.5MPa, stopping adding the initiator after 2 hours of reaction, and stopping adding the tetrafluoroethylene monomer after the reaction is continued for 15 minutes. Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing milky white slurry in the kettle into a post-treatment system through a discharging valve, performing high-speed shearing, demulsification and condensation, filtering and separation to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the polymerized phosphonic acid precursor polymer. The perfluorophosphonate monomer and the perfluorosulfonyl fluoride vinyl ether monomer in the filtrate are recycled after being recovered by a recovery system.
Polymer data: warp F 19 NMR and IR analyses showed that the copolymer had a structure containing 70.25% by mole of polymerized units of tetrafluoroethylene, 7.25% by mole of polymerized units of perfluorovinyl ether phosphonate, 3.23% by mole of polymerized units of perfluorovinyl phosphonate, 19.27% by mole of polymerized units of perfluorosulfonyl fluoride, and the total ion exchange capacity of the resin was as follows: 1.28mmol/g dry resin.
GPC measured molecular weight was 32.5 ten thousand, and molecular weight distribution number was 1.45.
IR spectrogram: 1470cm -1 Is the s=o vibration absorption peak in sulfonyl fluoride; 1294cm -1 A vibration absorption peak for p=o in phosphonate; 1028cm-1 is the absorption peak of C-O-C bond, 1225 and 1150cm -1 The two strongest absorptions are caused by CF vibration; 984cm -1 is-CF 3 Vibration-induced; 720cm -1 、641cm -1 from-CF after tetrafluoroethylene copolymerization 2 -CF 2 Vibration absorption causes.
Example 4:
cleaning the reaction kettle, adding 5.0L deionized water, 150g sodium dodecyl benzene sulfonate and 105g nonylphenol polyoxyethylene ether NP-10 emulsifier, starting a stirring device, vacuumizing, filling high-purity nitrogen for three times, testing the oxygen content in the reaction kettle to be less than 1ppm, vacuumizing, and adding 1400g of perfluorovinyl ether phosphonate monomer (CF) into the reaction kettle through a liquid feed valve 2 ＝CF-O-CF 2 CF 2 -P＝O-(OCH 2 CH 3 ) 2 ) 225g of perfluorovinyl phosphonate monomer (CF) 2 ＝CF-(CF 2 ) 3 -P＝O-(OCH 3 ) 2 ) 225g of perfluorovinyl ether sulfonyl fluoride monomer (CF) 2 ＝CF-O-CF 2 CF 2 -SO 2 F) Then, tetrafluoroethylene monomer is filled into the reaction kettle until the pressure is 1.8MPa, the temperature is raised to 20 ℃, and a gas flowmeter is used for controlling the flow rate to be 30cm 3 Introducing 250mLN into the reaction kettle in the period of/min 2 F 2 Initiating polymerization reaction, continuously introducing tetrafluoroethylene monomer, keeping the reaction pressure at 1.8MPa, stopping adding an initiator after 4 hours of reaction, and stopping adding the tetrafluoroethylene monomer after the reaction is continued for 1 min. Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing milky white slurry in the kettle into a post-treatment system through a discharging valve, demulsifying and condensing through high-speed shearing or other well-known demulsifying modes, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the polymerized phosphonic acid precursor polymer. The perfluorophosphonate monomer and the perfluorosulfonyl fluoride vinyl ether monomer in the filtrate are recycled after being recovered by a recovery system.
Polymer data: warp F 19 NMR and IR analyses showed that the copolymer had a structure containing 67.34% by mole of polymerized units of tetrafluoroethylene, 20.00% by mole of polymerized units of perfluorovinyl ether phosphonate, 5.32% by mole of polymerized units of perfluorovinyl phosphonate, 7.34% by mole of polymerized units of perfluorosulfonyl fluoride, and the total ion exchange capacity of the resin was: 1.37mmol/g dry resin.
GPC measured molecular weight was 23.0 million, molecular weight distribution number 2.35.
IR spectrogram: 1470cm -1 Is the s=o vibration absorption peak in sulfonyl fluoride; 1295cm -1 A vibration absorption peak for p=o in phosphonate; 1030cm-1 is the absorption peak of C-O-C bond, 1234 and 1153cm -1 The two strongest absorptions are caused by CF vibration; 986cm -1 is-CF 3 Vibration-induced; 722cm -1 、640cm -1 from-CF after tetrafluoroethylene copolymerization 2 -CF 2 Vibration absorption causes.
Example 5:
cleaning a reaction kettle, adding 5.0L deionized water and 55g nano calcium carbonate, starting a stirring device, vacuumizing, filling high-purity nitrogen for replacement three times, testing that the oxygen content in the reaction kettle is below 1ppm, vacuumizing, and adding 175g of perfluorovinyl ether phosphonate monomer ((CF) into the reaction kettle through a liquid feed valve 2 ＝CF-O-CF 2 CF 2 -P＝O-(OCH 2 CH 3 ) 2 ) 225g of perfluorovinyl phosphonate monomer ((CF) 2 ＝CF-CF 2 CF 2 -P＝O-(OCH 2 CH 3 ) 2 ) 725g of perfluorovinyl ether sulfonyl fluoride monomer ((CF) 2 ＝CF-O-CF 2 CF 2 -SO 2 F) And then, filling tetrafluoroethylene monomer into the reaction kettle until the pressure is 4.2MPa, heating to 55 ℃, adding 450g of 10% ammonium persulfate aqueous solution by using a metering pump to initiate polymerization, continuously introducing tetrafluoroethylene monomer to keep the reaction pressure at 4.2MPa, stopping adding an initiator after 2 hours of reaction, and stopping adding tetrafluoroethylene monomer after the reaction is continued for 15 minutes. Cooling the reaction kettle through a cooling circulation system, recovering unreacted tetrafluoroethylene monomer through a recovery system, placing milky white slurry in the kettle into a post-treatment system through a discharging valve, filtering and separating to obtain white polymer powder, and drying in a 100 ℃ oven to obtain the polymerized phosphonic acid precursor polymer. The perfluorophosphonate monomer and the perfluorosulfonyl fluoride monomer in the filtrate are recycled after being recovered by a recovery system.
Polymer data: warp F 19 NMR and IR analyses showed that the copolymer had a fluorinated nuclear magnetic resonance value of 82.34% by mole of polymerized units of tetrafluoroethylene, 4.85% by mole of polymerized units of perfluorovinyl ether phosphonate, 3.14% by mole of polymerized units of perfluorovinyl phosphonate, 9.67% by mole of polymerized units of perfluorosulfonyl fluoride, and the total ion exchange capacity of the resin was: 0.92mmol/g dry resin.
GPC measured molecular weight was 35.8 million, molecular weight distribution number 1.65.
IR spectrogram: 1468cm -1 Is the s=o vibration absorption peak in sulfonyl fluoride; 1290cm -1 A vibration absorption peak for p=o in phosphonate; 1030cm-1 is the absorption peak of the C-O-C bond, 1230 and 1153cm -1 The two strongest absorptions are caused by CF vibration, 720cm -1 、640cm -1 from-CF after tetrafluoroethylene copolymerization 2 -CF 2 Vibration absorption causes.
Comparative example 1: A+D1
In order to compare the effect of introducing the copolymer structure into the perfluorovinyl phosphate structural unit on the improvement of the thermal stability of the perfluorinated ion polymer, 275g of perfluorovinyl ether phosphonate monomer (CF) was added under the polymerization conditions of example 5, without changing other temperatures, pressures, initiators, etc 2 ＝CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -P＝O-(OCH 3 ) 2 ) 550g of perfluorovinyl ether sulfonyl fluoride monomer (CF) 2 ＝CF-O-CF 2 CF 2 -SO 2 F) The polymerization reaction was carried out, followed by the same post-treatment process as in examples 1 to 6, such as flocculation separation drying, to obtain a resin precursor polymer.
Polymer data: warp F 19 The NMR and IR analyses showed that the polymer structure contained 80.23 mole percent of polymerized units of tetrafluoroethylene, 15.85 mole percent of polymerized units of perfluorovinyl ether phosphonate, 3.92 mole percent of polymerized units of perfluorosulfonyl fluoride, and the total ion exchange capacity of the resin was: 0.95mmol/g dry resin.
GPC measured molecular weight was 31.0 million, and molecular weight distribution number 1.49.
IR spectrogram: 1468cm -1 Is the s=o vibration absorption peak in sulfonyl fluoride; 1217cm -1 A vibration absorption peak for p=o in phosphonate; 1028cm-1 is the absorption peak of C-O-C bond, 1230 and 1150cm -1 The two strongest absorptions are caused by CF vibration, 720cm -1 、640cm -1 from-CF after tetrafluoroethylene copolymerization 2 -CF 2 Vibration absorption causes.
Comparative example 2A+B
In order to compare the effect of the introduction of the copolymer structure into the perfluorovinyl ether sulfonyl fluoride structural unit on the low temperature conductivity of the perfluorinated ionic polymer, the polymerization conditions of example 3 were employed, and only 375g of perfluorovinyl ether phosphonate monomer (CF 2 ＝CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -P＝O-(OCH 3 ) 2 ) 250g of perfluorovinyl phosphonate monomer (CF) 2 ＝CF-CF 2 -P＝O-(OCH 3 ) 2 ) The polymerization reaction was carried out, followed by the same post-treatment process as in examples 1 to 6, such as flocculation separation drying, to obtain a resin precursor polymer.
Polymer data: warp F 19 NMR and IR analyses showed that the polymer structure contained 75.62 mol% of polymerized units of tetrafluoroethylene, 17.09 mol% of polymerized units of perfluorovinyl ether phosphonate, 7.29 mol% of polymerized units of perfluorovinyl phosphonate, and the total ion exchange capacity of the resin was: 1.01mmol/g dry resin.
GPC measured molecular weight was 23.1 million, and molecular weight distribution number 1.27.
IR spectrogram: 1295cm -1 A vibration absorption peak for p=o in phosphonate; 1238 and 1150cm -1 The two strongest absorptions are caused by CF vibration, 1033cm-1 is the absorption peak of P-O-C ether bond, 724cm -1 、642cm -1 from-CF after tetrafluoroethylene copolymerization 2 -CF 2 Vibration absorption causes.
Application example 1:
this application example is used to illustrate the process of trans-salifying and acidifying polymeric phosphonic acid precursor polymers.
The polymerized phosphonic acid precursor polymer obtained in examples 1-5 was added to a transformation tank of a 20% potassium hydroxide solution at a temperature of 70℃and heated for 48 hours to obtain the sulfonyl fluoride (-SO) 2 F) The side group is converted into potassium sulfonate (-SO) 3 K) Form (-PO (OR) in phosphonate ester 2 ) The side group is converted into potassium phosphitePO 3 K 2 )。
Washing the resin after salt conversion with pure water for 8 times, adding into nitric acid solution, and adding nitric acid solution (HNO) with nitric acid concentration of 15% by mass 3 ) After 4 times of replacement of the acid liquor by a residence time of 4 hours in the acid liquor at 60 ℃, the acid liquor is rinsed for 4 hours with deionized water at 50 ℃ in a high-purity water tank, and sodium sulfonate (-SO) in the polymer is removed 3 K) The side groups being converted to sulphonate ions (-SO) 3 H) Form (-PO) in sodium phosphonite 3 K 2 ) The side group is converted into phosphorous acid (-PO) 3 H 2 ) To obtain polymeric phosphonic acid resins (M1-M5).
The above operation was repeated for the resin precursor polymer obtained in comparative example 1-2 to obtain a resin polymer (D1-D2).
The resin polymer after the salt conversion and acidification of application example 1 was subjected to performance tests of tensile strength, resistivity, thermal decomposition temperature and glass transition temperature.
The tensile strength testing method comprises the following steps: GB/T1040-92.
The resistivity test method comprises the following steps: the resin polymer is processed by a melt extruder to obtain a film with the thickness of 25 mu m, and the film is obtained by testing by an electrochemical impedance tester under the conditions of T=155 ℃, T=105 ℃ and T=25 ℃ and 50%RH respectively, and the part 3 of the proton exchange membrane fuel cell is referred to national standard GB/T20042.3-2009: proton exchange membrane testing method.
The method for testing the thermal decomposition temperature comprises the following steps: the thermogravimetric curve was tested with TG.
The glass transition temperature is measured using a DMA test.
The test samples were respectively polymerized phosphonic acid resins (M1-M5) obtained by the salt conversion and acidification of application example 1, and resin polymers (D1-D2) obtained by the salt conversion and acidification.
The thermal decomposition temperature of the resin polymer D1 is 359 ℃ and the resistivity at high temperature is higher than that of the polymeric phosphonic acid resin (M1-M5); the resistivity of the resin polymer D2 is up to 102.04 omega cm at 25 ℃; the performance data of the polymeric phosphonic resins (M1-M5) are shown in table 1.
TABLE 1 Properties of polymeric phosphonic acid resins
As shown in Table 1, the thermal decomposition temperature measured by M1-M5 is 365-395 ℃, which is obviously improved compared with D1, because the invention adopts the perfluorovinyl ether phosphonate monomer, and meanwhile, the perfluorovinyl phosphonate monomer and the perfluorovinyl ether sulfonyl fluoride monomer are synergistic, and the polymerization unit of all C-C bonds is introduced into the side chain, so that the thermal stability of the whole polymerization type phosphonic acid resin is improved.
The resistivity of M1-M5 is obviously lower than D2 at 25 ℃, because the invention adopts the synergistic effect of the perfluorovinyl ether phosphonic acid polymerization unit, the perfluorovinyl phosphoric acid polymerization unit and the perfluorovinyl ether sulfonic acid polymerization unit in a certain range, so that the resistivity of the polymerized phosphonic acid resin at room temperature is reduced together, and the temperature interval of the polymerized phosphonic acid resin is widened.
Example 6:
2kg of a mixed solution of water and n-propanol was prepared, wherein the mass fraction of water was 30%. The resin (410 g) prepared in example 1 was added to the above mixed solution, and then transferred to an autoclave, and after sealing, stirring under nitrogen protection, heating to 180 ℃, keeping the temperature for 4 hours, cooling to room temperature, taking out the mixed solution, and after extraction and separation by carbon tetrachloride at room temperature and normal pressure, taking out the lower solution, thus obtaining a dispersion liquid with a solid content of 22%.
Example 7:
2kg of a mixed solution of water, isopropanol and DMF was prepared (wherein the mass ratio of isopropanol to DMF was 2:1), and the mass fraction of water was 36%. Adding the resin (400 g) prepared in the example 1 into the mixed solution, transferring into an autoclave, sealing, introducing nitrogen for protection, stirring, heating to 220 ℃, preserving heat for 5 hours, cooling to room temperature, taking out the mixed solution, extracting and separating the mixed solution by carbon tetrachloride at normal temperature and normal pressure, and taking out the lower layer solution to obtain the resin solution with 20% of solid content.
Example 8:
2kg of a mixed solution of water, ethanol and ethylene glycol was prepared (wherein the mass ratio of ethanol to ethylene glycol was 1:1), and the mass fraction of water was 50%. Adding the resin (590 g) prepared in the example 1 into the mixed solution, transferring into an autoclave, sealing, introducing nitrogen for protection, stirring, heating to 200 ℃, preserving heat for 4 hours, cooling to room temperature, taking out the mixed solution, extracting and separating by carbon tetrachloride at normal temperature and normal pressure, and taking out the lower solution to obtain the dispersion liquid with 30% of solid content.
Example 9:
2kg of a mixed solution of water, DMF and cyclohexanone was prepared (wherein the mass ratio of DMF to cyclohexanone was 5:1), and the mass fraction of water was 32%. Adding the resin (495 g) prepared in the example 4 into the mixed solution, transferring into an autoclave, sealing, introducing nitrogen for protection, stirring, heating to 190 ℃, preserving heat for 6 hours, cooling to room temperature, taking out the mixed solution, extracting and separating by carbon tetrachloride at normal temperature and normal pressure, and taking out the lower layer solution to obtain the film-forming resin dispersion liquid with the solid content of 25%.
Comparative example 3
2kg of a mixed solution of water and isopropyl alcohol was prepared, wherein the mass fraction of water was 67%, and a perfluorosulfonic acid resin (390 g) having an exchange capacity of 1.1mmol/g was added thereto, and the structure wasThen transferring into an autoclave, sealing, introducing nitrogen, stirring under protection, heating to 280 ℃, preserving heat for 8 hours, cooling to room temperature, taking out the mixed solution, extracting and separating by carbon tetrachloride at normal temperature and normal pressure, and taking out the lower layer solution, thus obtaining the resin solution with 20% of solid content after stirring and dispersing uniformly.
Comparative example 4
2kg of a mixed solution of water and glycol was prepared, wherein the mass fraction of water was 58%, and a perfluorosulfonic acid resin (490 g) having an exchange capacity of 1.2mmol/g was added thereto, and the structure was that Then transferring into autoclave, sealingStirring under nitrogen protection, heating to 250 ℃, preserving heat for 10 hours, cooling to room temperature, taking out the mixed solution, extracting and separating by carbon tetrachloride at normal temperature and normal pressure, and taking out the lower layer solution to obtain the resin solution with the solid content of 30%.
Application example 2
The dispersions prepared in examples 6 to 9 and comparative examples 3 and 4 were knife coated to form a film, and the solvent was heated to evaporate to form a film, thereby obtaining a proton exchange membrane of 12. Mu.m.
Performance testing is carried out on the prepared resin solution and the proton exchange membrane to obtain performance data shown in table 2, and the performance testing method is as follows:
the solid content of the resin dispersion liquid is tested by adopting a halogen analysis tester, and the micelle size is tested by adopting a Brookhaven particle size analyzer. The smaller the ionomer micelle particle size in the resin dispersion, the more uniform the catalyst dispersion and the higher the proton conductivity of the catalytic layer.
TABLE 1 resin solution Performance data for examples 6-9 and comparative examples 3, 4
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Claims (18)

1. The polymeric phosphonic acid resin with wide temperature range is characterized by comprising a fluorine-containing olefin unit, a perfluorovinyl ether phosphoric acid unit, a perfluorovinyl phosphoric acid unit and a perfluorovinyl ether sulfonic acid unit, wherein the polymeric phosphonic acid resin has the following structural formula:
；
Wherein k is an integer of 0 to 3, and f is an integer of 1 to 4; g is an integer of 0 to 4; t is an integer of 0 to 3, v is an integer of 1 to 4; a. b and c are integers from 1 to 20, a ', b ' and c ' are integers from 1 to 3; r is- (OCF) 2 ) m (CF 2 ) n X, X is Cl or F, m and n are integers of 0-3; x, y, z satisfy the following
Piece (2): x/(x+y+z) =0.1 to 0.5, y/(x+y+z) =0.1 to 0.5, and z/(x+y+z) =0.1 to 0.6.
2. The broad temperature zone polymeric phosphonic acid resin of claim 1 wherein the broad temperature zone polymeric phosphonic acid resin is derived from a polymeric phosphonic acid precursor polymer formed from copolymerization of fluoroolefin monomers, perfluorovinyl ether phosphonate monomers, perfluorovinyl phosphonate monomers, and perfluorosulfonyl fluoride vinyl ether monomers by a inversion reaction, the polymeric phosphonic acid precursor polymer having repeating units of:
；
wherein k is an integer of 0 to 3, and f is an integer of 1 to 4; g is an integer of 0 to 4; t is an integer of 0 to 3, v is an integer of 1 to 4; a. b and c are integers from 1 to 20, a ', b ' and c ' are integers from 1 to 3; wherein R is- (OCF) 2 ) m (CF 2 ) n X, X is Cl or F, m and n are integers of 0-3; the molar ratio of x, y and z satisfies the following conditions: x/(x+y+z) =0.1 to 0.5, y/(x+y+z) =0.1 to 0.5, and z/(x+y+z) =0.1 to 0.6;
p is an integer of 1 to 6, and q is an integer of 1 to 6.
3. The wide temperature range polymeric phosphonic acid resin of claim 2 wherein k=0-1, f=2, g=2, t=0-1, v=2, p=1-3, q=1-3 of the repeat units of the polymeric phosphonic acid precursor polymer.
4. The broad temperature range polymeric phosphonic acid resin of claim 2 wherein,
the structural formula of the perfluorovinyl ether phosphonate monomer is as follows:
；
where k=an integer from 0 to 3, f=an integer from 1 to 4, and p=an integer from 1 to 6;
the structural formula of the perfluorovinyl phosphonate monomer is as follows:
；
wherein g=an integer of 0 to 4, q=an integer of 1 to 6;
the structural formula of the perfluorosulfonyl fluoride vinyl ether monomer is as follows:
；
where t=an integer from 0 to 3 and v=an integer from 1 to 4.
5. The broad temperature range polymeric phosphonic acid resin of claim 4 wherein the perfluorovinyl ether phosphonate monomer has a structural formula wherein k=an integer from 0 to 1, f=2, and p=an integer from 1 to 3;
g=an integer of 0-2, q=an integer of 1-3 in the structural formula of the perfluorovinyl phosphonate monomer;
in the structural formula of the perfluorosulfonyl fluoride vinyl ether monomer, t=an integer of 0-1, and v=2.
6. The wide temperature range polymeric phosphonic acid resin of claim 2 wherein the polymeric phosphoric acid precursor copolymer comprises the following mole percent of polymerized units: the fluorine-containing olefin polymerization unit accounts for 50-85% of the total mole fraction, the perfluorovinyl ether phosphonate polymerization unit accounts for 2-25% of the total mole fraction, the perfluorovinyl phosphonate polymerization unit accounts for 2-25% of the total mole fraction, and the perfluorosulfonyl fluoride vinyl ether polymerization unit accounts for 1-25% of the total mole fraction.
7. The wide temperature range polymeric phosphonic acid resin of claim 6 wherein the polymeric phosphonic acid precursor copolymer comprises the following mole percent of polymerized units: the fluorine-containing olefin polymerization unit accounts for 60-85% of the total mole fraction, the perfluorovinyl ether phosphonate polymerization unit accounts for 5-20% of the total mole fraction, the perfluorovinyl phosphonate polymerization unit accounts for 5-20% of the total mole fraction, and the perfluorosulfonyl fluoride vinyl ether polymerization unit accounts for 5-20% of the total mole fraction.
8. A process for preparing the polymeric phosphonic acid resin according to claim 1, characterized in that the process comprises the following steps:
s1: carrying out copolymerization reaction on fluorine-containing olefin, perfluoro vinyl ether phosphonate monomer, perfluoro vinyl phosphonate monomer and perfluoro sulfonyl fluoride vinyl ether monomer under the action of an initiator to obtain a polymerized phosphonic acid precursor polymer;
s2: and soaking the prepared polymerized phosphonic acid precursor polymer in alkali liquor for transformation reaction, filtering after the transformation reaction is finished, pickling, and washing with water to obtain the polymerized phosphonic acid resin.
9. The method for producing a polymeric phosphonic acid resin according to claim 8, characterized in that in step S1, the reaction time of the copolymerization reaction is 0.5 to 48 hours, the reaction temperature is 0 to 100 ℃, and the reaction pressure is 0.01 to 10MPa.
10. The method for producing a polymeric phosphonic acid resin according to claim 9, characterized in that in step S1, the reaction time is 0.5 to 24 hours, the reaction temperature is 10 to 80 ℃, and the reaction pressure is 0.2 to 5MPa.
11. The method for producing a polymeric phosphonic acid resin according to claim 8, characterized in that in step S1, the initiator is one or more selected from the group consisting of perfluoroalkyl peroxides, azo compounds or persulfates, and redox systems.
12. The method for producing a polymeric phosphonic acid resin of claim 8 characterized in that in step S1 the copolymerization reaction comprises: solution polymerization in a fluorine-containing solvent, emulsion polymerization in an aqueous phase, or suspension polymerization in an aqueous phase.
13. The method for producing a polymeric phosphonic acid resin according to claim 12 characterized in that in the solution polymerization reaction, the fluorine-containing solvent is a solvent or solvents of a fluorinated liquid compound or oligomer containing no chlorine atom or any combination thereof.
14. The method for preparing a polymeric phosphonic acid resin according to claim 12, characterized in that the specific step of emulsion polymerization or suspension polymerization comprises:
1) Adding pure water, perfluorovinyl ether phosphonate monomer, perfluorovinyl phosphonate monomer, perfluorosulfonyl fluoride vinyl ether monomer, emulsifier/dispersant into a reaction kettle;
2) Filling fluorine-containing olefin into the reaction kettle through a gas metering groove;
3) After the temperature of the reaction kettle is raised, adding an initiator into the reaction system through a metering pump to initiate the reaction, and continuously adding a fluorine-containing olefin monomer and the initiator into the reaction kettle to maintain the reaction pressure of the reaction kettle;
4) Stopping adding the initiator and the fluorine-containing olefin monomer into the reaction kettle when the reaction is finished; the method comprises the steps of obtaining polymer slurry, enabling liquid slurry to enter post-treatment equipment through an emptying system, filtering and separating to obtain white polymer powder, and drying to obtain a polymerized phosphonic acid precursor polymer;
wherein, in the step 1), an emulsifier is selected when the copolymerization reaction is emulsion polymerization; dispersing agent is selected when the reaction is suspension polymerization.
15. The method for preparing polymeric phosphonic acid resin according to claim 14, wherein the emulsifier is one or any combination of anionic, nonionic or reactive emulsifiers;
the dispersing agent is one or any combination of inorganic salt powder and organic polymer;
The mass percentage concentration of the dispersing agent/emulsifying agent in water is 0.01-40%, the mass percentage concentration of the perfluorovinyl ether phosphonate monomer in water is 5-60%, the mass percentage concentration of the perfluorovinyl phosphate monomer in water is 5-60%, and the mass percentage concentration of the perfluorosulfonyl fluoride vinyl ether monomer in water is 1-60%.
16. The method for producing a polymeric phosphonic acid resin according to claim 15, characterized in that the concentration of the dispersant/emulsifier is 0.1 to 20% by mass, the concentration of the perfluorovinyl ether phosphonate monomer is 5 to 50% by mass, the concentration of the perfluorovinyl phosphate monomer is 5 to 50% by mass, and the concentration of the perfluorosulfonyl fluoride vinyl ether monomer is 5 to 50% by mass.
17. The method for producing a polymeric phosphonic acid resin according to claim 8 characterized in that the reaction time for transformation is 1 to 144 hours and the transformation temperature is 20 to 150 ℃;
the pickling time is 1-144 hours, and the pickling temperature is 20-150 ℃;
in the step S2, the mass ratio of the polymerized phosphonic acid precursor polymer to the alkali liquor is 1 (1-10);
the alkali liquor is sodium hydroxide, potassium hydroxide solution or lithium hydroxide, ammonia water, sodium carbonate, potassium carbonate or lithium carbonate; the acid washing solution is protonic acid or a mixed solution of protonic acid.
18. The method for producing a polymeric phosphonic acid resin according to claim 17 characterized in that the reaction time for transformation is 5 to 72 hours and the transformation temperature is 20 to 100 ℃;
the pickling time is 5-72h, and the pickling temperature is 20-100 ℃.
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