CN115716887B - Perfluorinated sulfonic acid resin and preparation method and application thereof - Google Patents
Perfluorinated sulfonic acid resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a perfluorinated sulfonic acid resin and a preparation method and application thereof, belonging to the technical field of proton exchange membranes for fuel cells and perfluorinated ion membranes for chlor-alkali. The perfluorinated sulfonic acid resin is obtained by initiating polymerization reaction by using tetrafluoroethylene, perfluorinated alpha-olefin and perfluorinated sulfonyl vinyl ether monomer as comonomers and water and hydrofluoroether as solvents. The invention also provides a preparation method of the perfluorinated sulfonic acid resin, which comprises the following steps: mixing water, perfluoro alpha-olefin, perfluoro sulfonyl vinyl ether, emulsifier and hydrofluoroether, then charging tetrafluoroethylene gas, and adding initiator to react at the reaction temperature of 40-120 ℃ and the reaction pressure of 2-10 MPa to obtain the perfluoro sulfonic acid resin. The invention also provides application of the perfluorinated sulfonic acid resin or the perfluorinated sulfonic acid resin prepared by the preparation method in preparation of an ion exchange membrane. The invention realizes high conversion rate of sulfonyl fluoride vinyl ether monomer in the perfluorinated sulfonic acid resin.
Description
Technical Field
The invention relates to the technical field of proton exchange membranes for fuel cells and perfluorinated ion membranes for chlor-alkali, in particular to perfluorinated sulfonic acid resin and a preparation method and application thereof.
Background
The perfluorinated sulfonic acid resin is a copolymer of tetrafluoroethylene monomer and perfluorinated sulfonyl vinyl ether monomer, and is widely applied to the fields of proton exchange membrane fuel cells, chlor-alkali industry, energy storage batteries, organic synthesis catalysts and the like. The prior art includes solution polymerization in fluorocarbon solvents, suspension polymerization in water, dispersion polymerization, emulsion polymerization, bulk polymerization, and the like. The ratio of tetrafluoroethylene monomer to perfluorosulfonyl vinyl ether monomer during polymerization determines the ratio of tetrafluoroethylene to perfluorosulfonyl vinyl ether monomer in the polymer produced, but since the reactivity ratio of the two monomers differs greatly under the same conditions, it has been found that about 1 perfluorosulfonyl vinyl ether molecule is bonded to about every 5 to 6 TFE (tetrafluoroethylene) molecules, because the reactivity of tetrafluoroethylene monomer is much higher than that of perfluorosulfonyl vinyl ether monomer in the copolymerization reaction. Therefore, a large amount of ether monomer is usually required to be added in the polymerization reaction, but only a part of ether monomer still reacts, a large amount of unreacted ether monomer is required to be separated and reused after the reaction is finished, and the separation and recovery process increases the manufacturing cost, so that the economic benefit for preparing the perfluorinated sulfonic acid resin with high ion exchange capacity is low, and the mass production of the perfluorinated sulfonic acid resin with high exchange capacity is not facilitated.
The main application of the perfluorinated sulfonic acid resin is to prepare an ion exchange membrane, wherein the ion exchange membrane is a membrane material with ion conducting capacity, and the ion conductivity and the resistance are indexes for measuring the performance of the material. The ionic conductivity is generally expressed in terms of EW values, which are expressed as the weight of the resin containing 1 mole of sulfonate groups, and IEC values, which are expressed as per gram of H + The equivalent exchange millimole number of the dry film and the corresponding ion of the external solution is carried out, IEC=1000/EW, the higher the PSVE conversion rate in the polymerization process is, the higher the content of sulfonate groups is, the lower the EW value is, the higher the IEC value is, the formed polymer has higher ion conductivity, the stronger the ion exchange capacity of the polymer is, and the prepared film has good conductivity; the smaller the value of the internal resistance, the higher the performance when used as a fuel cell, and the application in the fields of fuel cells, chlor-alkali industry and the like is more advantageous. In US 5281680, with TFE and sulfonyl fluoride type vinyl ether as comonomers, a solution polymerization process is used, with an EW value of 1000g/mol when the molar ratio of TFE to sulfonyl fluoride type vinyl ether is 5.6:1, and with an EW value of 2 when the molar ratio of TFE monomer to sulfonyl fluoride type vinyl ether monomer: in the process 1, the EW value is 650g/mol, a large amount of PSVE monomers are added in the polymerization process, and the obtained perfluorosulfonic acid resin has low EW value. In US 3884885, perfluorosulfonic resins of high EW values are obtained when the molar ratio of TFE to sulfonyl fluoride vinyl ether is 7.5:1, using short side chain sulfonyl fluoride monomers, under equivalent conditionsThe perfluorosulfonic acid resin with lower EW value prepared by the method has low reaction activity of sulfonyl fluoride monomers, a large amount of sulfonyl fluoride monomers are needed to be added in the polymerization reaction, and the EW value of the perfluorosulfonic acid resin finally obtained is high. In CN114276482A, TFE, cyclic sulfonyl fluoride-type vinyl ether monomer and CF 2 ＝CFO[CF 2 CF(CF3)O] a [CF2CF2] b SO 2 When F is copolymerized, when the molar ratio of TFE to the other two comonomers is 1:1-5:1, the EW value of the prepared polymer is 716-1257g/mol, although the novel cyclic monomer containing sulfonyl fluoride groups is selected, the conversion rate is very low in the polymerization process, a large amount of sulfonyl fluoride monomers still need to be added in the reaction process, and a large amount of sulfonyl fluoride monomers still need to be recovered after the reaction is finished, so that the production cost is greatly increased.
In CN 101709101A, the molar ratio of TFE, sulfonyl fluoride vinyl ether monomer and bromine side group vinyl ether monomer is 50-85:5-49:1-10, and the ion exchange capacity of the finally synthesized perfluorinated ion exchange resin is between 0.5 and 2.6mmol/g, and although the patent adopts short side group sulfonyl fluoride monomer with different structures for multi-copolymerization, the experimental result shows that: when the dosage of sulfonyl fluoride monomer is low, the IEC value of the prepared perfluorinated sulfonic acid resin is low. Low IEC values are detrimental to the preparation of ion exchange membranes in fuel cells and chlor-alkali cells. In the prior art, a large amount of sulfonyl fluoride vinyl ether monomer is added in the polymerization process, but the sulfonyl fluoride vinyl ether monomer which is actually reacted is few, a large amount of unreacted monomer still needs to be recovered after the reaction is finished, and the production cost is greatly increased in the recovery process.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a perfluorinated sulfonic acid resin, a preparation method and application thereof, and solves the technical problem of low conversion rate of sulfonyl fluoride vinyl ether monomers in the prior art.
In order to achieve the technical aim, the technical scheme of the invention provides a perfluorinated sulfonic acid resin, which is obtained by initiating polymerization reaction by using tetrafluoroethylene, perfluorinated alpha-olefin and perfluorinated sulfonyl vinyl ether monomer as comonomers and water and hydrofluoroether as solvents and using an initiator.
Further, the EW value of the perfluorinated sulfonic acid resin is 500-700g/mol.
Further, after the perfluorosulfonic acid resin is transformed into a perfluorosulfonic acid resin film, the perfluorosulfonic acid resin film has an electrical conductivity of 4.9 to 8.0mS/cm.
Further, the method comprises the steps of, the hydrofluoroether is perfluorobutyl methyl ether, 1, 3-hexafluoroisopropyl methyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and 1, 2-tetra-fluoroethyl ether one or more of fluoroethyl-2, 3-tetrafluoropropyl ether; and/or the initiator is one or more of perfluoroalkyl peroxide, perfluoroalkoxy peroxide and persulfate; preferably, the persulfate is ammonium persulfate; preferably, the perfluoroalkyl peroxide is one or two of a perfluorobutyryl peroxide compound and a perfluoropropoxypropyl peroxide compound.
Further, the structural formula of the perfluorosulfonyl vinyl ether is as follows: CF (compact flash) 2 ＝CF-O-[CF 2 CFO(CF 3 )] m (CF 2 ) p SO 2 F, wherein m is greater than or equal to 0 and m is an integer, p is greater than or equal to 0 and p is an integer.
Further, the perfluorosulfonyl vinyl ether is CF 2 ＝CF-O-[CF 2 CFO(CF 3 )](CF 2 ) 2 SO 2 F、CF 2 ＝CF-O-[CF 2 CFO(CF 3 )](CF 2 ) 5 SO 2 F and CF 2 ＝CF-O-(CF 2 ) 2 SO 2 F, one or more of the following.
Further, the molar ratio of the perfluoro alpha-olefin to the perfluoro sulfonyl vinyl ether monomer is 1 (2-10); and/or the molar ratio of the tetrafluoroethylene to the perfluoro alpha-olefin is (40-98): 1; and/or the molar ratio of the tetrafluoroethylene to the perfluorosulfonyl vinyl ether is (10-20): 1; and/or the molar ratio of the hydrofluoroether to the perfluorosulfonyl vinyl ether monomer is (1-10): 1; and/or the water is used in an amount of 1 to 15 times the total mass of the comonomer.
In addition, the invention also provides a preparation method of the perfluorinated sulfonic acid resin, which comprises the following steps: mixing water, perfluoro alpha-olefin, perfluoro sulfonyl vinyl ether, emulsifier and hydrofluoroether, then charging tetrafluoroethylene gas, and adding initiator to react at the reaction temperature of 40-120 ℃ and the reaction pressure of 2-10 MPa to obtain the perfluoro sulfonic acid resin.
Further, the emulsifier is one or more of perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkoxysulfonate and perfluorooctanoate, preferably, the perfluorooctanoate is ammonium perfluorooctanoate; and/or the emulsifier is used in an amount of 0.01 to 25wt% based on the mass of the water.
In addition, the invention also provides application of the perfluorinated sulfonic acid resin or the perfluorinated sulfonic acid resin prepared by the preparation method in preparation of the ion exchange membrane.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a perfluorinated sulfonic acid resin, which is prepared by taking tetrafluoroethylene, perfluoro alpha-olefin and perfluorinated sulfonyl vinyl ether monomer as comonomers, taking water and hydrofluoroether as solvents and initiating polymerization reaction by an initiator. The perfluorinated sulfonic acid resin has better chemical stability, lower EW value and higher electric conductivity under the coordination of the components.
Detailed Description
The specific embodiment provides a perfluorinated sulfonic acid resin, which is characterized in that tetrafluoroethylene, perfluorinated alpha-olefin and perfluorinated sulfonyl vinyl ether monomer are used as comonomers, water and hydrofluoroether are used as solvents, and polymerization reaction is initiated by an initiator to obtain the perfluorinated sulfonic acid resin; the perfluorosulfonic acidThe EW value of the acid resin is 500-700g/mol; after the perfluorinated sulfonic acid resin is converted into a perfluorinated sulfonic acid resin film, the conductivity of the perfluorinated sulfonic acid resin film is 4.9-8.0mS/cm; the hydrofluoroether is perfluorobutyl methyl ether, 1, 3-hexafluoroisopropyl methyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and 1, 2-tetra-fluoroethyl ether one or more of fluoroethyl-2, 3-tetrafluoropropyl ether; and/or the initiator is one or more of perfluoroalkyl peroxide, perfluoroalkoxy peroxide and persulfate; preferably, the persulfate is ammonium persulfate; preferably, the perfluoroalkyl peroxide is one or two of a perfluorobutyryl peroxide compound and a perfluoropropoxypropyl peroxide compound; the structural formula of the perfluorosulfonyl vinyl ether is as follows: CF (compact flash) 2 ＝CF-O-[CF 2 CFO(CF 3 )] m (CF 2 ) p SO 2 F, wherein m is more than or equal to 0 and m is an integer, p is more than or equal to 0 and p is an integer; the perfluorosulfonyl vinyl ether is CF 2 ＝CF-O-[CF 2 CFO(CF 3 )](CF 2 ) 2 SO 2 F、CF 2 ＝CF-O-[CF 2 CFO(CF 3 )](CF 2 ) 5 SO 2 F and CF 2 ＝CF-O-(CF 2 ) 2 SO 2 One or more of F; the molar ratio of the perfluoro alpha-olefin to the perfluoro sulfonyl vinyl ether monomer is 1 (2-10); and/or the molar ratio of the tetrafluoroethylene to the perfluoro alpha-olefin is (40-98): 1; and/or the molar ratio of the tetrafluoroethylene to the perfluorosulfonyl vinyl ether is (10-20): 1; and/or the molar ratio of the hydrofluoroether to the perfluorosulfonyl vinyl ether monomer is (1-10): 1; and/or the water is used in an amount of 1 to 15 times the total mass of the comonomer.
The specific embodiment also provides a preparation method of the perfluorinated sulfonic acid resin, which comprises the following steps: mixing water, perfluoro alpha-olefin, perfluoro sulfonyl vinyl ether, an emulsifier and hydrofluoroether, then filling tetrafluoroethylene gas, and adding an initiator to react for 0.5-48 h at the reaction temperature of 40-120 ℃ and the reaction pressure of 2-10 MPa to obtain perfluoro sulfonic acid resin; the emulsifier is one or more of perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkoxysulfonate and perfluorooctanoate, and preferably the perfluorooctanoate is ammonium perfluorooctanoate; and/or the emulsifier is used in an amount of 0.01 to 25wt% based on the mass of the water.
The invention adopts an emulsion polymerization method, has high polymerization speed and high product molecular weight, takes water as a main dispersion medium, is favorable for heat transfer and temperature control, and simultaneously adds the hydrofluoroether as a cosolvent, thereby increasing the solubility of PSVE monomers and TFE monomers, ensuring the uniform dispersion of a reaction system, improving the conversion rate of PSVE in the preparation process of the perfluorinated sulfonic acid resin, and simultaneously unexpectedly finding that the PSVE in the technical scheme of the invention can be uniformly dispersed in the resin, and the perfluorinated sulfonic acid resin has stable quality.
In addition, the conversion rate of the PSVE monomer is higher, and the addition amount of the PSVE monomer in the polymerization process is greatly reduced, so that the monomer recovery time is shortened, the production cost is reduced, and the method has higher economic benefit, and meanwhile, the obtained perfluorinated sulfonic acid resin with high exchange capacity is more important, and the obtained perfluorinated sulfonic acid resin has stable quality and high economic benefit.
The specific embodiment also provides application of the perfluorinated sulfonic acid resin or the perfluorinated sulfonic acid resin prepared by the preparation method in preparation of the ion exchange membrane.
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The reaction vessels used in each of the examples and comparative examples were, unless otherwise specified, 2L stainless steel autoclave equipped with a thermometer, a pressure gauge, a heater, a stirring paddle, an internal cooling water pipe, a liquid metering pump, a feed pipe and valve, a discharge pipe and valve, a mass flow meter, and the like. In addition, the PSVE in the following examples and comparative examples uses CF 2 ＝CF-O-[CF 2 CFO(CF 3 )](CF 2 ) 2 SO 2 F, moleculesThe amount is 446; it should be understood that other perfluorosulfonyl vinyl ethers of PSVE-like structure proposed in the present invention are also suitable for use in the present invention.
Example 1
The embodiment provides a perfluorinated sulfonic acid resin, which is prepared by the following steps:
repeatedly replacing a stainless steel high-pressure reaction kettle with nitrogen until the water content is detected to be below 20ppm, the oxygen content is below 10ppm, vacuumizing and filling tetrafluoroethylene monomer to 0.1MPa, vacuumizing to 0.0001MPa, adding 600g deionized water, 3.09g hexafluoropropylene (namely HFP), 90g perfluorosulfonyl vinyl ether, 50g perfluorobutyl methyl ether and 3g perfluoroalkyl sulfonate into the kettle, heating to 40 ℃, filling tetrafluoroethylene monomer to the pressure of 2.0MPa, adding 10ml ammonium persulfate with a metering pump, maintaining the reaction pressure at about 2.0MPa, adding 0.5g initiator into the reaction kettle every 10min, stopping adding the initiator after 2h, stopping adding tetrafluoroethylene monomer after the reaction is continued for 10min, adding 201.8g of tetrafluoroethylene monomer, putting the milky white slurry obtained by cooling and solidification into a post-treatment device through a discharging valve, and obtaining the sulfonyl fluoride type perfluorinated sulfonic resin after high-speed shearing, filtering separation and drying.
This example also includes the preparation of H-type perfluorosulfonic acid resin film from the sulfonyl fluoride-type perfluorosulfonic acid resin obtained by transformation.
The sulfonyl fluoride type perfluorinated sulfonic acid resin prepared in the embodiment is obtained through analysis and test: EW value is 640g/mol, conductivity is 5.3mS/cm at 60 ℃ and 100% relative humidity, and the prepared film is treated with Fenton reagent (3% hydrogen peroxide and 2mg/L FeSO) 4 ) The surface and internal structure changes are observed under an electron microscope after soaking, and the test result shows that the chemical stability is better.
In addition, the product prepared according to the embodiment has good quality stability, and the product is obtained through mass production experiment verification.
Example 2
The embodiment provides a perfluorinated sulfonic acid resin, which is prepared by the following steps:
repeatedly replacing a stainless steel high-pressure reaction kettle with nitrogen until the water content is detected to be below 20ppm, the oxygen content is below 10ppm, pumping/charging tetrafluoroethylene monomer to 0.1MPa, vacuumizing to 0.0001MPa, adding 800g of deionized water, 11.6g of hexafluoropropylene, 70g of perfluorosulfonyl vinyl ether, 280g of 1, 3-hexafluoroisopropyl methyl ether and 3g of perfluoroalkoxysulfonate into the kettle, heating to 120 ℃, charging tetrafluoroethylene monomer to the pressure of 10MPa, adding 3g of perfluorobutyryl peroxide compound by a metering pump, maintaining the reaction pressure at about 10MPa, adding 0.5g of initiator every 10min, stopping adding the initiator after the reaction is continued for 2h, stopping adding tetrafluoroethylene monomer after the reaction is continued for 10min, setting the total dosage of tetrafluoroethylene monomer to 312g, putting the cooled and coagulated milk-white slurry into post-treatment equipment through a discharge valve, and obtaining the sulfonyl fluoride-based perfluorobutyryl resin after high-speed shearing, filtering separation and drying.
This example also includes the preparation of H-type perfluorosulfonic acid resin film from the sulfonyl fluoride-type perfluorosulfonic acid resin obtained by transformation.
The sulfonyl fluoride type perfluorinated sulfonic acid resin prepared in the embodiment is obtained through analysis and test: EW value is 526g/mol, conductivity is 8.0mS/cm at 60 ℃ and 100% relative humidity, and the prepared film is treated with Fenton reagent (3% hydrogen peroxide and 2mg/L FeSO) 4 ) The surface and internal structure changes are observed under an electron microscope after soaking, and the test result shows that the chemical stability is better.
Example 3
The embodiment provides a perfluorinated sulfonic acid resin, which is prepared by the following steps:
repeatedly replacing a stainless steel high-pressure reaction kettle with nitrogen until the water content is detected to be below 20ppm, the oxygen content is below 10ppm, vacuumizing and filling tetrafluoroethylene monomer to 0.1MPa, vacuumizing to 0.0001MPa, adding 800g of deionized water, 5.6g of hexafluoropropylene, 100g of perfluorosulfonyl vinyl ether, 224g of 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and 3g of ammonium perfluorooctanoate into the kettle, heating to 80 ℃, filling tetrafluoroethylene monomer to the pressure of 6.0MPa, adding 5g of perfluoropropoxypropyl peroxide into the reaction kettle by using a metering pump, maintaining the reaction pressure of about 6.0MPa, supplementing 1g of initiator into the reaction kettle every 10min, stopping adding the initiator after the reaction is continued for 2h, stopping adding tetrafluoroethylene monomer after the reaction is continued for 10min, the total consumption of the tetrafluoroethylene monomer is 336g, putting the cooled and solidified milky white slurry into post-treatment equipment through a discharging valve, and obtaining the perfluorosulfonyl resin after high-speed shearing, filtering, separating and drying.
This example also includes the preparation of H-type perfluorosulfonic acid resin film from the sulfonyl fluoride-type perfluorosulfonic acid resin obtained by transformation.
The sulfonyl fluoride type perfluorinated sulfonic acid resin prepared in the embodiment is obtained through analysis and test: the EW value is 565g/mol, the conductivity is 7.4mS/cm at 60 ℃ and 100% relative humidity, and the prepared film is treated with Fenton reagent (3% hydrogen peroxide and 2mg/L FeSO) 4 ) The surface and internal structure changes are observed under an electron microscope after soaking, and the test result shows that the chemical stability is better.
Example 4
The embodiment provides a perfluorinated sulfonic acid resin, which is prepared by the following steps:
repeatedly replacing a stainless steel high-pressure reaction kettle with nitrogen until the water content is detected to be below 20ppm, the oxygen content is below 10ppm, vacuumizing and filling tetrafluoroethylene monomer to 0.1MPa, vacuumizing to 0.0001MPa, adding 1000g of deionized water, 9.6g of hexafluoropropylene, 200g of perfluorosulfonyl vinyl ether, 208g of 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether and 6g of ammonium perfluorooctanoate into the kettle, heating to 40 ℃, filling tetrafluoroethylene monomer to 3.0MPa, adding 10g of ammonium persulfate by a metering pump, maintaining the reaction pressure to be about 3.0MPa, adding 1g of initiator into the reaction kettle every 10min, stopping adding the initiator after the reaction is continued for 10min, stopping adding tetrafluoroethylene monomer, setting the total dosage of the tetrafluoroethylene monomer to 448g, putting the cooled and coagulated slurry into post-treatment equipment through a discharge valve, and obtaining the sulfonyl fluoride resin after high-speed shearing, filtering separation and drying.
This example also includes the preparation of H-type perfluorosulfonic acid resin film from the sulfonyl fluoride-type perfluorosulfonic acid resin obtained by transformation.
The sulfonyl fluoride type perfluorinated sulfonic acid resin prepared in the embodiment is obtained through analysis and test: EW value is 603g/mol, conductivity is 6.5mS/cm at 60 ℃ and 100% relative humidity, and the prepared film is treated with Fenton reagent (3% hydrogen peroxide and 2mg/L FeSO) 4 ) The surface and internal structure changes are observed under an electron microscope after soaking, and the test result shows that the chemical stability is better.
Example 5
This example shows a perfluorosulfonic acid resin which is different from example 1 only in that the amount of perfluorobutyl methyl ether added is small, 20g, and other raw materials and amounts, and reaction conditions are the same as in example 1.
The sulfonyl fluoride type perfluorinated sulfonic acid resin prepared in the embodiment is obtained through analysis and test: EW value is 680g/mol, conductivity is 4.8mS/cm at 60 ℃ and 100% relative humidity, and the prepared film is treated with Fenton reagent (3% hydrogen peroxide and 2mg/L FeSO) 4 ) The surface and internal structure changes are observed under an electron microscope after soaking, and the test result shows that the chemical stability is better.
Example 6
This example shows a perfluorosulfonic acid resin which differs from example 2 only in that the amount of 1, 3-hexafluoroisopropyl methyl ether added is small, 100g, and other raw materials and amounts, and reaction conditions are the same as in example 2.
The sulfonyl fluoride type perfluorinated sulfonic acid resin prepared in the embodiment is obtained through analysis and test: EW value is 615g/mol, conductivity is 6.2mS/cm at 60 ℃ and 100% relative humidity, and the prepared film is treated with Fenton reagent (3% hydrogen peroxide and 2mg/L FeSO) 4 ) The surface and internal structure changes are observed under an electron microscope after soaking, and the test result shows that the chemical stability is better.
Comparative example 1
This comparative example proposes a perfluorosulfonic acid resin which differs from example 3 only in that 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether is not added, and other raw materials and amounts, and reaction conditions are the same as in example 3.
Comparative example 2
This comparative example proposes a perfluorosulfonic acid resin which differs from example 4 only in that 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether is not added, and other raw materials and amounts, and reaction conditions are the same as in example 4.
Comparative example 3
This comparative example proposes a perfluorosulfonic acid resin which differs from example 1 only in that perfluorodimethylbutane is substituted for perfluorobutyl methyl ether in the same molar amount, and other raw materials, amounts and reaction conditions are the same as in example 1.
EW values and conductivity of the perfluorosulfonic acid resins produced in comparative examples 1 to 3 were also measured, and the results are shown in Table 1.
TABLE 1 raw materials of examples 1-6 and comparative examples 1-3, EW values and conductivities
It should be noted that the above EW value and conductivity detection method is as follows:
EW value: after the prepared perfluorosulfonic acid ion exchange membrane is dried to constant weight in vacuum at 80 ℃, 1-2 g is precisely weighed, placed in a 250ml triangular flask, added with 50ml of 1mol/LNaoH aqueous solution, fully stirred, placed overnight, titrated to pink with 0.1mol/LNaoH standard solution as an indicator by taking phenolphthalein as an end point, and the EW value is calculated according to the following formula:wherein V is NaOH For the volume of NaOH solution consumed, C NaOH Is the molar concentration of NaOH solution, m is hydrogen ion type perfluorinated sulfonic acid ionThe weight of the dry film was exchanged.
Conductivity: the electrode A, B is used for pressing the perfluorosulfonic acid ion exchange membrane, direct current is loaded on the electrode A, B, the current and voltage drop passing through the membrane can be measured by an ammeter and a voltmeter in a loop, and the conductivity is calculated according to the following formula:where σ is the film conductivity, L is the measured film thickness, R is the film resistance, and A is the area.
As can be seen from the test results in Table 1, examples 1-6 have good dissolution of PSVE monomer by using hydrofluoroether as a cosolvent, and under the cooperation of the components, the conversion rate of PSVE in the perfluorosulfonic acid resin can be greatly improved, and comparative examples 1 and 5 and comparative examples 2 and 6 can show that the conversion rate of PSVE can be improved along with the increase of the addition amount of the hydrofluoroether; in addition, comparative examples 1 and 5 and comparative examples 2 and 6 show that the addition of hydrofluoroethers can also affect the conversion of PSVE, with less hydrofluoroethers being detrimental to PSVE conversion. From the test results of comparative examples 1 and 2, it can be seen that the EW value and conductivity of the obtained product were higher and lower without adding a hydrofluoroether, and from the test results of example 1 and comparative example 3, it can be seen that both the EW value and conductivity of the perfluorosulfonic acid resin obtained by adding perfluorobutyl methyl ether were significantly better than those of the perfluorosulfonic acid resin obtained by adding perfluorodimethyl cyclobutane.
According to the invention, the hydrofluoroether is added into the raw material formula as the cosolvent by adopting the emulsion polymerization method, the cosolvent contains a fluorocarbon chain structure, and has good dissolving action on PSVE and TFE, compared with the traditional method which uses water as the solvent, especially PSVE, the solvent in the cosolvent is good, even the solvent can be completely dissolved mutually, the participation reaction rate and the utilization rate of the perfluorosulfonyl vinyl ether monomer can be greatly improved under the cooperation of the raw materials, and the PSVE can more uniformly disperse the reaction system, so that the preparation of the perfluorosulfonic resin with high ion exchange capacity and high chemical stability is facilitated, and the prepared resin has stable quality and is favorable for industrial production. The polymerization speed is high, the molecular weight of the product is high, the danger is low, the production cost is reduced, the discharge amount of three wastes in production can be reduced, and the subsequent processes such as condensation, washing, dehydration, drying and the like are still needed.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (12)
1. A perfluorinated sulfonic acid resin is characterized in that tetrafluoroethylene, perfluorinated alpha-olefin and perfluorinated sulfonyl vinyl ether monomer are used as comonomers, water and hydrofluoroether are used as solvents, and an initiator is used for initiating emulsion polymerization reaction to obtain the perfluorinated sulfonic acid resin; the molar ratio of the perfluoro alpha-olefin to the perfluoro sulfonyl vinyl ether monomer is 1 (2-10); the molar ratio of the tetrafluoroethylene to the perfluoro alpha-olefin is (40-98): 1; the molar ratio of the tetrafluoroethylene to the perfluorosulfonyl vinyl ether is (10-20): 1; the molar ratio of the hydrofluoroether to the perfluorosulfonyl vinyl ether monomer is (1-10) 1; the water is used in an amount of 1 to 15 times the total mass of the comonomer.
2. The perfluorosulfonic acid resin according to claim 1, characterized in that the perfluorosulfonic acid resin has an EW value of 500 to 700g/mol.
3. The perfluorosulfonic acid resin according to claim 1, wherein after the perfluorosulfonic acid resin is converted into a perfluorosulfonic acid resin film, the perfluorosulfonic acid resin film has an electrical conductivity of 4.9 to 8.0mS/cm.
4. A perfluorosulfonic acid resin according to claim 1, characterized in that, the hydrofluoroether is 1, 3-hexafluoroisopropyl methyl ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and 1, 2-tetra-fluoroethyl ether one or more of fluoroethyl-2, 3-tetrafluoropropyl ether; and/or the initiator is one or more of perfluoroalkyl peroxide, perfluoroalkoxy peroxide and persulfate.
5. The perfluorosulfonic acid resin according to claim 4, wherein the perfluoroalkyl peroxide is one or both of a perfluorobutyryl peroxide compound and a perfluoropropoxypropyl peroxide compound.
6. The perfluorosulfonic acid resin according to claim 4, wherein the persulfate is ammonium persulfate.
7. The perfluorosulfonic acid resin according to claim 1, wherein the perfluorosulfonyl vinyl ether has the structural formula:wherein m is equal to or greater than 0 and m is an integer, p is equal to or greater than 0 and p is an integer.
8. The perfluorosulfonic acid resin according to claim 7, wherein the perfluorosulfonyl vinyl ether is、/>And->One or more of the following.
9. A method for producing the perfluorosulfonic acid resin according to any one of claims 1 to 8, comprising: mixing water, perfluoro alpha-olefin, perfluoro sulfonyl vinyl ether, an emulsifier and hydrofluoroether, then filling tetrafluoroethylene gas, and adding an initiator to react at the reaction temperature of 40-120 ℃ and the reaction pressure of 2-10 MPa to obtain the perfluoro sulfonic acid resin.
10. The method for producing a perfluorosulfonic acid resin according to claim 9, wherein the emulsifier is one or more of a perfluoroalkylcarboxylate, a perfluoroalkylsulfonate, a perfluoroalkoxysulfonate, and a perfluorooctanoate.
11. The method for producing a perfluorosulfonic acid resin according to claim 10, wherein the perfluorooctanoic acid salt is ammonium perfluorooctanoate; and/or the emulsifier is used in an amount of 0.01 to 25wt% based on the mass of the water.
12. Use of a perfluorosulfonic acid resin according to any one of claims 1 to 8 or a perfluorosulfonic acid resin prepared by a preparation method according to any one of claims 9 to 11 in the preparation of an ion exchange membrane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127430A (en) * | 1998-12-16 | 2000-10-03 | 3M Innovative Properties Company | Microemulsions containing water and hydrofluroethers |
| CN113795519A (en) * | 2019-05-08 | 2021-12-14 | 大金工业株式会社 | Method for producing fluoropolymer and fluoropolymer |
| CN114085309A (en) * | 2021-11-22 | 2022-02-25 | 浙江巨化技术中心有限公司 | Solution polymerization preparation method of perfluorosulfonic acid resin |
| CN114835842A (en) * | 2022-06-15 | 2022-08-02 | 浙江巨化技术中心有限公司 | Polymerization method of perfluorosulfonyl fluororesin |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60135080D1 (en) * | 2000-12-26 | 2008-09-11 | Asahi Glass Co Ltd | Solid polymer electrolyte material, liquid composition, solid polymer fuel cell and fluoropolymer |
| JP2010501673A (en) * | 2006-08-24 | 2010-01-21 | スリーエム イノベイティブ プロパティズ カンパニー | Method for producing fluoropolymer |
| CN103347908B (en) * | 2010-12-17 | 2017-02-08 | 3M创新有限公司 | Microemulsions and fluoropolymers made using microemulsions |
| WO2020116652A1 (en) * | 2018-12-07 | 2020-06-11 | Ａｇｃ株式会社 | Production method of fluorine-containing polymer containing fluorosulfonyl group, production method of fluorine-containing polymer containing salt-type sulfonic acid group, and production method of fluorine-containing polymer containing acid-type sulfonic acid group |
| CN114651352A (en) * | 2019-10-21 | 2022-06-21 | Ａｇｃ株式会社 | Fluorosyl group-containing fluorine-containing polymer and method for producing the same, sulfonyl group-containing fluorine-containing polymer and method for producing the same, solid polymer electrolyte membrane, membrane/electrode assembly, and solid polymer fuel cell |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127430A (en) * | 1998-12-16 | 2000-10-03 | 3M Innovative Properties Company | Microemulsions containing water and hydrofluroethers |
| CN113795519A (en) * | 2019-05-08 | 2021-12-14 | 大金工业株式会社 | Method for producing fluoropolymer and fluoropolymer |
| CN114085309A (en) * | 2021-11-22 | 2022-02-25 | 浙江巨化技术中心有限公司 | Solution polymerization preparation method of perfluorosulfonic acid resin |
| CN114835842A (en) * | 2022-06-15 | 2022-08-02 | 浙江巨化技术中心有限公司 | Polymerization method of perfluorosulfonyl fluororesin |
Non-Patent Citations (1)
| Title |
|---|
| 全氟磺酰树脂研究进展;王文瀚等;《有机氟工业》;第18-22页 * |
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