Fluorosulfonyl group-containing compound, fluorosulfonyl group-containing monomer, and their production methods

Abstract

A method for producing a fluorosulfonyl group-containing compound to obtain a compound represented by the following formula 5 from a compound represented by the following formula 1 as a starting material and a method for producing a fluorosulfonyl group-containing monomer in which the fluorosulfonyl group-containing compound is used: ##STR00001##
wherein R.sup.1 and R.sup.2 are a C.sub.1-3 alkylene group, and R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

Claims

1. A method for producing a fluorosulfonyl group-containing compound, which comprises: reacting a compound represented by the following formula 1 with a sulfonating agent to obtain a compound represented by the following formula 2, reacting the compound represented by the following formula 2 with a chlorinating agent to obtain a compound represented by the following formula 3, reacting the compound represented by the following formula 3 with a fluorinating agent to obtain a compound represented by the following formula 4, and subjecting the compound represented by the following formula 4 to fluorination treatment to obtain a compound represented by the following formula 5: ##STR00036## wherein R.sup.1 and R.sup.2 are a C.sub.1-3 alkylene group, and R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

2. A method for producing a fluorosulfonyl group-containing monomer, which comprises: obtaining the compound represented by the formula 5 by the method for producing a fluorosulfonyl group-containing compound as defined in claim 1, and reacting the compound represented by the formula 5 with a perfluoroallylating agent to obtain a compound represented by the following formula 7: ##STR00037## wherein R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

3. A method for producing a fluorosulfonyl group-containing monomer, which comprises: obtaining the compound represented by the formula 5 by the method for producing a fluorosulfonyl group-containing compound as defined in claim 1, adding 2 moles of hexafluoropropylene oxide to 1 mole of the compound represented by the formula 5 in the presence of a metal fluoride to obtain a compound represented by the following formula 8a, and thermally decomposing the compound represented by the following formula 8a to obtain a compound represented by the following formula 9a: ##STR00038## wherein R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

4. A method for producing a fluorosulfonyl group-containing monomer, which comprises obtaining the compound represented by the formula 5 by the method for producing a fluorosulfonyl group-containing compound as defined in claim 1, adding 1 mole of hexafluoropropylene oxide to 1 mole of the compound represented by the formula 5 in the presence of a metal fluoride to obtain a compound represented by the following formula 8b, and thermally decomposing the compound represented by the following formula 8b to obtain a compound represented by the following formula 10: ##STR00039## wherein R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

5. A method for producing a fluorosulfonyl group-containing monomer, which comprises reacting a compound represented by the following formula 5 with a perfluoroallylating agent to obtain a compound represented by the following formula 7: ##STR00040## wherein R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

6. A method for producing a fluorosulfonyl group-containing monomer, which comprises adding 2 moles of hexafluoropropylene oxide to 1 mole of a compound represented by the following formula 5 in the presence of a metal fluoride to obtain a compound represented by the following formula 8a, and thermally decomposing the compound represented by the following formula 8a to obtain a compound represented by the following formula 9a: ##STR00041## wherein R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

7. A method for producing a fluorosulfonyl group-containing monomer, which comprises adding 1 mole of hexafluoropropylene oxide to 1 mole of a compound represented by the following formula 5 in the presence of a metal fluoride to obtain a compound represented by the following formula 8b, and thermally decomposing the compound represented by the following formula 8b to obtain a compound represented by the following formula 10: ##STR00042## wherein R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

8. A fluorosulfonyl group-containing compound, which is either one or both of a compound represented by the following formula 5 and a compound represented by the following formula 5′: ##STR00043## wherein R.sup.F1 and R.sup.F2 are a CF.sub.2 group.

9. A fluorosulfonyl group-containing monomer, which is a compound represented by the following formula 7: ##STR00044## wherein R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

10. A fluorosulfonyl group-containing monomer, which is a compound represented by the following formula 10: ##STR00045## wherein R.sup.F1 and R.sup.F2 are a C.sub.1-3 perfluoroalkylene group.

Description

EXAMPLES

(1) Now, the present invention will be described with reference to Examples, but the present invention is not limited thereto. Further, Ex. 1 is an Example of the present invention, and Ex. 2 to 13 are Reference Examples.

.SUP.1.H-NMR

(2) .sup.1H-NMR was measured under conditions of frequency of 300.4 MHz and chemical shift reference of tetramethylsilane. Unless otherwise specified, CD.sub.3CN was used as a solvent. The quantitative measurement of a product was conducted by results of .sup.1H-NMR analysis and the amount of an added internal standard sample (1,3-bis(trifluoromethyl)benzene).

.SUP.19.F-NMR

(3) .sup.19F-NMR was measured under conditions of frequency of 282.7 MHz, a solvent of CD.sub.3CN and chemical shift reference of CFCl.sub.3. The quantitative measurement of a product was conducted by results of .sup.19F-NMR and the amount of an added internal standard sample (1,3-bis(trifluoromethyl)benzene).

.SUP.13.C-NMR

(4) .sup.13C-NMR was measured under conditions of frequency of 75.5 MHz and chemical shift reference of tetramethylsilane. Unless otherwise specific, CD.sub.3CN was used as a solvent.

Yield

(5) The yield is (yield of a reaction step)×(yield of a purification step), and the reaction yield is the yield of a reaction step before purifying a desired product, which excludes the loss in the purification step.

Ion Exchange Capacity

(6) A membrane of a polymer (polymer F or polymer H) was vacuum dried at 120° C. for 12 hours. The mass of the dried membrane of the polymer was measured, and then the membrane of the polymer was immersed in a 0.85 mol/g sodium hydroxide solution (solvent:water/methanol=10/90 (mass ratio)) to hydrolyze ion exchange groups. The sodium hydroxide solution after the hydrolysis was back titrated with 0.1 mol/L hydrochloric acid to obtain the ion exchange capacity (meq/g dry resin) of the polymer.

Proportion of Units Based on Fluorosulfonyl Group-Containing Monomer

(7) The proportions of units based on the fluorosulfonyl group-containing monomer (SO.sub.2F group-containing monomer) in the polymer F was calculated from the ion exchange capacity of the polymer F.

TQ Value

(8) The polymer F was melt extruded by means of a flow tester (CFT-500A, manufactured by Shimadzu Corporation) provided with a nozzle having a length of 1 mm and an internal diameter of 1 mm under an extrusion pressure of 2.94 MPa (gage pressure) while changing the temperature. The temperature (TQ value) at which the extruded amount of the polymer F became 100 mm.sup.3/s was obtained. The higher the TQ value is, the larger the molecular weight of the polymer is.

Measurement of Dynamic Viscoelasticity

(9) The dynamic viscoelasticity of the membrane of the polymer F or the membrane of the polymer H was measured by means of a dynamic viscosity measuring apparatus (DVA-225, manufactured by IT Keisoku Seigyo) under conditions of test specimen width: 5.0 mm, length of specimen between grips: 15 mm, measuring frequency: 1 Hz, rate of temperature rise: 2° C./min and a tensile mode. Tan σ (loss tangent) was calculated from the ratio (E″/E′) of the loss elastic modulus E′ to the storage elastic modulus E′, and tan σ-temperature curve was drawn. The value of a peak temperature between −100 to 200° C. on the tan σ-temperature curve is Tg of the polymer F or a softening temperature of the polymer H. Further, a storage elastic modulus E′-temperature curve was drawn, and a value of the storage elastic modulus at 120° C. was taken as a 120° C. storage elastic modulus of the polymer H.

Conductivity

(10) To a membrane of the polymer H having a thickness of 25 μm and a width of 5 mm, a substrate provided with 4 terminal electrodes at an interval of 5 mm was contact-bonded by known four probe method, and the resistance of the membrane of the polymer H was measured at an alternative current: 10 kHz and a voltage: 1 V under the constant temperature and constant humidity conditions of temperature: 80° C. and relative humidity of 50% to calculate the conductivity.

Moisture Content

(11) The membrane of the polymer H was immersed in warm water of 80° C. for 16 hours and cooled until the water temperature reached at most 25° C. The membrane of the polymer H was taken out, water droplets attached on a surface of the membrane were wiped away by a filter paper, and the mass W1 of the membrane of the polymer H was measured. The membrane of the polymer H was dried in a glove box under a nitrogen atmosphere for 48 hours, and then the mass W2 of the membrane of the polymer H was measured in the glove box. The moisture content (mass standard) was obtained by the following formula I.
Moisture content=(W1−W2)/W2×100  Formula 1

Abbreviations

(12) PSVE: CF.sub.2═CFOCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2SO.sub.2F, P2SVE: CF.sub.2═CFOCF.sub.2CF(CF.sub.2OCF.sub.2CF.sub.2SO.sub.2F)OCF.sub.2CF.sub.2SO.sub.2F, PDD: perfluoro-2,2-dimethyl-1,3-dioxole, PMVE: perfluoro(methyl vinyl ether), PFtBPO: (CF.sub.3).sub.3COOC(CF.sub.3).sub.3, AlBN: (CH.sub.3).sub.2C(CN)N═NC(CH.sub.3).sub.2(CN), IPP: (CH.sub.3).sub.2CHOC(O)OOC(O)OCH(CH.sub.3).sub.2, V-601: CH.sub.3OC(O)C(CH.sub.3).sub.2—N═N—C(CH.sub.3).sub.2C(O)OCH.sub.3, PFB: (C.sub.3F.sub.7C(O)O).sub.2, HFC-52-13p: CF.sub.3(CF.sub.2).sub.5H, HFE-347pc-f: CF.sub.3CH.sub.2OCF.sub.2CF.sub.2H, HCFC-225cb: CClF.sub.2CF.sub.2CHClF, HCFC-141b: CH.sub.3CCl.sub.2F.

Ex. 1

Ex. 1-1

(13) 560 g of chlorosulfuric acid was charged in a 2 L four-necked flask provided with a stirrer, a condenser, a thermometer and a dropping funnel under nitrogen gas sealing. The flask was cooled in an ice bath, and a mixed liquid of 139.5 g of the compound 1-1 and 478.7 g of dichloromethane was dropwise added over 20 minutes, while maintaining the internal temperature at 20° C. Heat generation and generation of gas were observed at the time of the dropwise addition. After completion of the dropwise addition, the flask was set in an oil bath, and a reaction was carried out for 7 hours while maintaining the internal temperature at from 30 to 40° C. The reaction proceeded with the generation of gas, and a white solid precipitated. After the reaction, the inside of the flask was decompressed to distill dichloromethane off. A yellowish white solid remained in the flask. The solid was analyzed by .sup.1H-NMR, and formation of compound 2-1 was confirmed.

(14) ##STR00029##

(15) NMR spectrum of compound 2-1; .sup.1H-NMR (solvent: D.sub.2O): 4.27 ppm (—CH.sub.2—, 4H, s). .sup.13C-NMR (solvent: D.sub.2O): 62.6 ppm (—CH.sub.2—), 195.3 ppm (C═O).

Ex. 1-2

(16) the compound 2-1 obtained in Ex. 1-1 was used in a subsequent reaction as it was without being isolated. 2,049 g of thionyl chloride was added in the flask of Ex. 1-1. The flask was heated to 80° C., followed by reflux for 15 hours. Along with the progress of the reaction, the reflux temperature increased from 52° C. to 72° C. The generation of gas was observed during the reaction. The termination of the reaction was when the compound 2-1 was entirely dissolved, and the generation of gas terminated. The reaction liquid was transferred to a 2 L separable flask, and the flask was left to cool for 9 hours while a gas phase part was sealed with nitrogen gas, and as a result, a blackish brown solid precipitated in the separable flask. Unreacted thionyl chloride was removed by decantation. Toluene was added to wash the precipitated solid, and toluene was removed by decantation again. Washing with toluene was carried out three times in total, and the amount of used toluene was 1,207 g in total. The precipitated solid was dried at 25° C. for 71 hours under nitrogen gas stream. The dried solid was recovered and analyzed by .sup.1H-NMR, and it was confirmed that 356.5 g of compound 3-1 with a purity of 96.2% was obtained. The yield on the compound 1-1 basis was 56.0%.

(17) ##STR00030##

(18) NMR spectrum of compound 3-1; .sup.1H-NMR: 5.20 ppm (—CH.sub.2—, 4H, s). .sup.13C-NMR: 72.3 ppm (—CH.sub.2—), 184.6 ppm (C═O).

Ex. 1-3

(19) 90.0 g of the compound 3-1 and 750 mL of acetonitrile were charged in a 1 L four-necked flask provided with a stirrer, a condenser and a thermometer under nitrogen gas sealing. The flask was cooled in an ice bath, and 110.3 g of potassium hydrogen fluoride was added with stirring. Heat generation due to the addition was slight. The ice bath was changed to a water bath, and a reaction was carried out for 62 hours while maintaining the internal temperature at from 15 to 25° C. Along with the reaction, fine white solids formed. The reaction liquid was transferred to a pressure filter, and unreacted potassium hydrogen fluoride was removed from the product by filtration. Acetonitrile was added to the filter, the solid remaining on the filter was washed until the filtrate became transparent, and the wash was recovered. The filtrate and the wash were subjected to an evaporator to distill acetonitrile off. 950 mL of toluene was added to the remaining dried solid, followed by heating to 100° C. to dissolve the solid in toluene. The solution was natural filtered to remove undissolved components. The filtrate was transferred to a 1 L separable flask, and the flask was left to cool for 14 hours while a gas phase part was sealed with nitrogen gas, and as a result, pale brown needle crystals precipitated in the separable flask. The crystals were washed with toluene and dried at 25° C. for 30 hours under nitrogen gas stream. The dried solid was recovered and analyzed by .sup.1H-NMR and .sup.19F-NMR, and as a result, it was confirmed that 58.1 g of compound 4-1 with a purity of 97.6% was obtained. The yield on the compound 3-1 basis was 72.3%.

(20) ##STR00031##

(21) NMR spectrum of compound 4-1; .sup.1H-NMR: 4.97 ppm (—CH.sub.2—, 4H, d, J=3.1 Hz). .sup.19F-NMR: 62.4 ppm (—SO.sub.2F, 2F, t, J=3.1 Hz). .sup.13C-NMR: 60.7 ppm (—CH.sub.2—), 184.9 ppm (C═O).

Ex. 1-4

(22) 9.93 g of the compound 4-1 and 89.7 g of acetonitrile were charged in a 200 mL autoclave made of nickel. The autoclave was cooled, nitrogen gas was fed at a flow rate of 6.7 L/hr while maintaining the internal temperature at from 0 to 5° C., and the reaction liquid was bubbled for 1 hours. While maintaining the temperature of the reaction liquid at from 0 to 5° C., a mixed gas of fluorine gas and nitrogen gas (mixing ratio=10.3 mol %/89.7 mol %) was introduced over 6 hours at a flow rate of 6.7 L/hr. Nitrogen gas was fed again at a flow rate of 6.7 L/hr, and the reaction liquid was bubbled for 1 hour. 103.2 g of the reaction liquid was recovered from the autoclave. The reaction liquid was analyzed by .sup.19F-NMR, and it was confirmed that 8.4 mass % of compound 5-1 and 3.2 mass % of hydrogen fluoride were contained. The reaction yield on the compound 4-1 basis was 66%.

(23) ##STR00032##

(24) NMR spectrum of compound 5-1 (in the presence of hydrogen fluoride); .sup.19F-NMR: −104.1 ppm (—CF.sub.2—, 4F, s), 45.8 ppm (—SO.sub.2F, 2F, s).

Ex. 1-5

(25) 19.9 g of the compound 4-1 and 85.6 g of acetonitrile were charged in a 200 mL autoclave made of nickel. The autoclave was cooled, nitrogen was fed at a flow rate of 6.7 L/hr while maintaining the internal temperature at from 0 to 5° C., and the reaction liquid was bubbled for 1 hour. While maintaining the temperature of the reaction liquid at from 0 to 5° C., a mixed gas of fluorine gas and nitrogen gas (mixing ratio=10.3 mol %/89.7 mol %) was introduced at a flow rate of 16.4 L/hr over 6.5 hours. Nitrogen gas was fed again at a flow rate of 6.7 L/hr, and the reaction liquid was bubbled for 1 hour. 109.6 g of the reaction liquid containing the compound 5-1 was recovered from the autoclave.

Ex. 1-6

(26) 20.1 g of the compound 4-1 and 80.1 g of acetonitrile were charged in a 200 mL autoclave made of nickel. The autoclave was cooled, nitrogen gas was fed at a flow rate of 6.7 L/hr while maintaining the internal temperature at from 0 to 5° C., and the reaction liquid was bubbled for 1 hour. While maintaining the temperature of the reaction liquid at from 0 to 5° C., a mixed gas of fluorine gas and nitrogen gas (mixing ratio=20.0 mol %/80.0 mol %) was introduced at a flow rate of 8.4 L/hr over 6 hours. Nitrogen gas was fed again at a flow rate of 6.7 L/hr, and the reaction liquid was bubbled for 1 hour. 107.1 g of the reaction liquid containing the compound 5-1 was recovered from the autoclave.

Ex. 1-7

(27) 1.65 g of potassium fluoride and 7.8 mL of diethylene glycol dimethyl ether (diglyme) were charged in a 50 mL four-necked flask provided with a stirrer, a condenser, a thermometer and a dropping funnel. The flask was cooled in an ice bath, and 8.43 g of the reaction liquid obtained in Ex. 1-4 was dropwise added by means of a plastic syringe while maintaining the internal temperature at from 0 to 10° C. by stirring. Intense heat generation was observed, and 15 minutes was spent for the dropwise addition. After completion of the dropwise addition, the ice bath was changed to a water bath, and the reaction was carried out for 1 hour at from 15 to 20° C. The flask was cooled in an ice bath again, and 6.56 g of compound 6-1 was dropwise added from a dropping funnel while maintaining the temperature of the reaction liquid at from 0 to 10° C. After completion of the dropwise addition, the ice bath was changed to a water bath, and the reaction was carried out for 3.5 hours at from 20 to 25° C. By-products were removed from the reaction liquid by suction filtration to recover the filtrate. The solid removed by filtration was washed with an appropriate amount of acetonitrile, and the wash and the filtrate were mixed. 37.1 g of the filtrate was quantitatively analyzed by .sup.19F-NMR, and it was confirmed that 2.04 mass % of compound 7-1 was contained. The reaction yield on the compound 4-1 basis was 46.6%.

(28) ##STR00033##

(29) NMR spectrum of compound 7-1; .sup.19F-NMR: −191.5 ppm (CF.sub.2═CF—, 1F, ddt, J=116, 38, 14 Hz), −133.8 ppm (—O—CF—, 1F, tt, J=21.3, 6.1 Hz), −103.1 ppm (—CF.sub.2—SO.sub.2F, 4F, m), −101.5 ppm (CF.sub.2═CF—, 1F, ddt, J=116, 49, 27 Hz), −87.6 ppm (CF.sub.2═CF—, 1F, ddt, J=49, 38, 7 Hz), −67.5 ppm (—CF.sub.2—O—, 2F, m), 46.8 ppm (—SO.sub.2F, 2F, s).

Ex. 1-8

(30) 36.6 g of potassium fluoride and 125.6 g of acetonitrile were charged in a 500 mL four-necked flask provided with a stirrer, a condenser, a thermometer and a dropping funnel. The flask was cooled in an ice bath, and 79.8 g of the reaction liquid obtained in Ex. 1-5 was dropwise added by means of a dropping funnel made of a plastic while maintaining the internal temperature at from 0 to 10° C. by stirring. Intense heat generation was observed, and 23 minutes was spent for the dropwise addition. After completion of the dropwise addition, the ice bath was changed to a water bath, and the reaction was carried out for 5.5 hour at from 20 to 30° C. The flask was cooled in an ice bath again, and 146.0 g of the compound 6-1 was dropwise added from a dropping funnel while maintaining the temperature of the reaction liquid at from 0 to 10° C. After completion of the dropwise addition, the ice bath was changed to a water bath, and the reaction was carried out for 16 hours at from 15 to 25° C. Suction filtration was carried out in the same manner as in Ex.7-1, and 412.3 g of the obtained filtrate was quantitatively analyzed by .sup.19F-NMR, and it was confirmed that 3.93 mass % of the compound 7-1 was contained. The reaction yield on the compound 4-1 basis was 55.9%. The filtrate was distilled off under reduced pressure to isolate the compound 7-1 as a fraction with a boiling point of 97.2° C./10 KPa. The purity by gas chromatography was 98.0%.

Ex. 1-9

(31) 3.70 g of potassium fluoride and 10.9 g of acetonitrile were charged in a 50 mL four-necked flask provided with a stirrer, a condenser, a thermometer and a dropping funnel. The flask was cooled in an ice bath, and 10.2 g of the reaction liquid obtained in Ex. 1-6 was dropwise added by means of a plastic syringe while maintaining the internal temperature at from 0 to 10° C. by stirring. Intense heat generation was observed, and 8 minutes was spent for the dropwise addition. After completion of the dropwise addition, the ice bath was changed to a water bath, and the reaction was carried out for 3 hours at from 20 to 30° C. The flask was cooled in an ice bath again, and 14.6 g of the compound 6-1 was dropwise added from a dropping funnel while maintaining the temperature of the reaction liquid at from 0 to 10° C. After completion of the dropwise addition, the ice bath was changed to a water bath, and the reaction was carried out for 17 hours at from 15 to 25° C. Suction filtration was carried out in the same manner as in Ex.7-1, and 55.9 g of the obtained filtrate was quantitatively analyzed by .sup.19F-NMR, and it was confirmed that 4.77 mass % of the compound 7-1 was contained. The reaction yield on the compound 4-1 basis was 69.6%. Further, the reaction yield on the compound 1-1 basis (the reaction yield in all steps for preparing the monomer) was 28.2%.

Ex. 2

Ex. 2-1

(32) 70.0 g of the compound 7-1 was added in an autoclave (internal capacity of 100 mL and made of stainless steel), followed by cooling and deaerating by liquid nitrogen. 2.53 g of TFE was introduced in the autoclave, and the autoclave was heated in an oil bath until the internal temperature reached 100° C. The pressure at that time was 0.29 MPaG (gage pressure). A mixed liquid of 36.3 mg of PFtBPO as a polymerization initiator and 2.58 g of HFC-52-13p was injected into the autoclave. Further, nitrogen gas was introduced from an injection line to completely inject the liquid in the injection line into the autoclave. TFE in the gas phase part was diluted by this operation, and as a result, the pressure increased to 0.56 MPaG. While maintaining the pressure at 0.56 MPaG, TFE was continuously added to carry out polymerization. The inside of the autoclave was cooled to terminate the polymerization, when the added amount of TFE reached 4.03 g after 9.5 hours, and the gas in the system was purged. The reaction liquid was diluted with HFC-52-13p, HFE-347pc-f was added to aggregate the polymer, and the polymer was filtered. Then, an operation of stirring the polymer in HFC-52-13p and aggregating the polymer with HFE-347pc-f again was repeated twice. Vacuum drying at 120° C. was carried out to obtain polymer F-1 which is a copolymer of TFE and the compound 7-1. Results are shown in Table 1.

Ex. 2-2 to Ex. 2-5

(33) Polymer F-2 to polymer F-5 were obtained in the same manner as in Ex. 2-1, except that conditions were changed as shown in Table 1 (in Ex. 2-2, 34.0 g of HFC-52-13p was charged with the compound 7-1, and 2.9 g was used to prepare a mixed liquid with the polymerization initiator, and in Ex. 2-3 to Ex. 2-5, without initially charging TFE, and instead, after heating to the polymerization temperature, TFE was injected until the pressure reached the pressure prior to nitrogen gas dilution as shown in Table 1). Results are shown in Table 1.

(34) TABLE-US-00001 TABLE 1 Ex. 2-1 Ex. 2-2 Ex. 2-3 Ex. 2-4 Ex. 2-5 Obtained polymer F F-1 F-2 F-3 F-4 F-5 Capacity of reactor [mL] 100 100 100 100 100 Compound 7-1 [g] 70.0 31.5 103.0 80.0 82.0 Initially charged TFE [g] 2.53 2.44 — — — HFC-52-13p [g] 2.58 36.9 6.46 4.23 4.18 Polymerization initiator PFtBPO PFtBPO PFtBPO PFtBPO PFtBPO Amount of polymerization initiator 36.3 34.3 105.8 41.4 42.3 [mg] Polymerization temperature [° C.] 100 100 100 100 100 Pressure prior to nitrogen gas 0.29 0.27 0.10 0.29 0.25 dilution [MPaG] Polymerization pressure [MPaG] 0.56 0.56 0.60 0.56 0.49 Continuously added TFE [g] 4.03 4.29 3.84 5.59 6.49 Polymerization time [hr] 9.5 8.5 12.5 6.9 10.0 Yield of polymer F [g] 6.4 4.6 7.61 8.47 10.0 Ion exchange capacity [meq/g dry 1.87 1.49 2.37 1.78 1.90 resin] Units based on compound 7-1 13.8 10.0 19.9 12.4 14.0 [mol %] Units based on compound 7-1 41.2 32.8 52.2 38.4 41.8 [mass %] TQ value [° C.] 238 268 158 298 314 Tg [° C.] 39 43 33 41 39

Ex. 3

Ex. 3-1 to Ex. 3-5

(35) Membranes of polymers H-1 to H-5 were obtained by the following method using the polymers F-1 to F-5.

(36) A polymer F was press molded at a temperature higher by 10° C. than TQ value (260° C. in Ex. 3-4 and Ex. 3-5) under 4 MPa (gage pressure) to obtain a membrane (thickness of from 100 to 250 μm) of the polymer F. The membrane of the polymer F was immersed in an alkali aqueous solution as shown in Table 2 at 80° C. for 16 hours to hydrolyze and thereby convert —SO.sub.2F groups in the polymer F into —SO.sub.3K groups. Further, the membrane of the polymer was immersed in a 3 mol/L hydrochloric acid aqueous solution at 50° C. for 30 minutes and then immersed in ultrapure water at 80° C. for 30 minutes. A cycle of immersing in a hydrochloric acid aqueous solution and immersing in ultrapure water was carried out five times in total to convert —SO.sub.3K groups in the polymer into —SO.sub.3H groups. The washing with ultrapure water was repeated, until pH of water in which the membrane of the polymer was immersed became 7. The membrane of the polymer was sandwiched between filter papers and air-dried to obtain a membrane of polymer H. Results are shown in Table 2.

(37) TABLE-US-00002 TABLE 2 Ex. 3-1 Ex. 3-2 Ex. 3-3 Ex. 3-4 Ex. 3-5 Used polymer F F-1 F-2 F-3 F-4 F-5 Obtained polymer H H-1 H-2 H-3 H-4 H-5 Used alkali aqueous Aqueous Aqueous Aqueous Aqueous Aqueous solution solution A solution B solution A solution C solution A Softening temperature 147 151 151 151 153 [° C.] Elastic modulus at 95.7 160 72.1 119 117 120° C. [MPa] Conductivity [S/cm] 0.136 0.080 0.164 0.123 0.136 Moisture content [%] 136 48 At least 93 110 400

(38) In Table 2, “aqueous solution A” is potassium hydroxide/water=20/80 (mass ratio), “aqueous solution B” is potassium hydroxide/dimethylsulfoxide/water=15/30/55 (mass ratio), and “aqueous solution C” is potassium hydroxide/methanol/water=15/20/65 (mass ratio). Further, these definitions are also applied to the after-described Table 4.

Ex. 4

Ex. 4-1

(39) 123.8 g of PSVE, 35.2 g of HCFC-225cb and 63.6 mg of AlBN were added in a hastelloy autoclave having an internal capacity of 230 mL, followed by cooling and deaeration by liquid nitrogen. The temperature was raised to 70° C., and TFE was introduced in the system to maintain the pressure at 1.14 MPaG. TFE was continuously added so as to maintain the constant pressure at 1.14 MPaG. After 7.9 hours, when the amount of added TFE reached 12.4 g, the autoclave was cooled, and gas in the system was purged to terminate the reaction. The polymer solution was diluted with HCFC-225cb, and HCFC-141b was added for aggregation. Washing with HCFC-225cb and HCFC-141b was carried out, followed by drying to obtain 25.1 g of polymer F′-1 which is a copolymer of TFE and PSVE. Results are shown in Table 3.

Ex. 4-2 to Ex. 4-4

(40) TFE and PSVE or P2SVE were copolymerized in the same manner as in Ex. 4-1 to obtain polymers F′-2 to F′-4, except that respective conditions were changed as shown in Table 3. Results are shown in Table 3.

(41) TABLE-US-00003 TABLE 3 Ex. 4-1 Ex. 4-2 Ex. 4-3 Ex. 4-4 Obtained polymer F F′-1 F′-2 F′-3 F′-4 Capacity of reactor [mL] 230 230 1,000 1,000 SO.sub.2F group-containing monomer PSVE PSVE P2SVE P2SVE Amount of SO.sub.2F group-containing 123.8 159.0 901.7 328.0 monomer [g] HCFC-225cb [g] 35.2 0.8 0 415.5 Polymerization initiator AIBN IPP IPP V-601 Amount of polymerization initiator [mg] 63.6 47.9 90.7 223.7 Polymerization temperature [° C.] 70 40 40 70 Polymerization pressure [MPaG] 1.14 0.46 0.55 0.69 Polymerization time [hr] 7.9 13.6 7.0 3.7 Yield of polymer F [g] 25.1 28.1 64.8 104.1 Ion exchange capacity [meq/g dry resin] 1.10 1.44 1.87 1.46 Units based on SO.sub.2F group-containing 17.7 28.5 18.3 11.8 monomer [mol %] Units based on SO.sub.2F group-containing 48.8 63.9 58.2 45.4 monomer [mass %] TQ value [° C.] 225 238 296 241 Tg [° C.] 8 1 −1 7

Ex. 5

Ex. 5-1 to Ex. 5-4

(42) The polymers F′-1 to F′-4 were treated to obtain membranes of polymer H′-1 to H′-4 in the same manner as in Ex. 3. Results are shown in Table 4.

(43) TABLE-US-00004 TABLE 4 Ex. 5-1 Ex. 5-2 Ex. 5-3 Ex. 5-4 Used polymer F′ F′-1 F′-2 F′-3 F′-4 Obtained polymer H′ H′-1 H′-2 H′-3 H′-4 Used alkaline aqueous solution Aqueous Aqueous Aqueous Aqueous solution A solution C solution B solution C Softening temperature [° C.] 99 97 133 138 Elastic modulus at 120° C. [MPa] 2.70 1.81 12.5 40.8 Conductivity [S/cm] 0.050 0.089 0.151 0.102 Moisture content [%] 66 89 164 82

(44) It is evident from Tables 1 to 4 that the compound 7-1 has a small molecular weight and has two SO.sub.2F groups, whereby even if the proportion of units based on the SO.sub.2F group-containing monomer in the polymer F obtained by copolymerization with TFE is made to be lower than that of the conventional polymer F′, a polymer H having the ion exchange capacity at the same level can be obtained. The polymer F thereby has a high Tg, and the handling efficiency and the storage stability of the polymer F will improve. The polymer H has a high softening temperature for the same reason. Further, the polymer H has a low moisture content per ion exchange capacity, whereby a membrane of the polymer H which maintains the mechanical strength up to a high temperature can be formed. Further, the amount of expensive SO.sub.2F group-containing monomer to be used for the polymer F can be reduced as compared with the conventional polymer F′, whereby the membrane of the polymer H can be produced at a low cost. On the other hand, in a case where the proportion of units based on the SO.sub.2F group-containing monomer in the polymer F is the same as the conventional polymer F′, the ion exchange capacity of the polymer H can be increased, whereby a membrane of the polymer H which has a higher ion conductivity than the conventional polymer H′, can be obtained.

Ex. 6

Ex. 6-1

(45) 4.3 g of a membrane of the polymer H being cut into small pieces and 75 g of ultrapure water were added in a 100 mL container made of a polytetrafluoroethylene (PTFE), followed by heating at 200° C. for 24 hours. The contents were transferred to a tray made of PTFE and air-dried under nitrogen stream at 30° C. for 64 hours. 200 mL of the dried polymer H-1 was transferred in an autoclave made of glass, and 21.4 g of a mixed solvent of ultrapure water/ethanol (50/50 (mass ratio)) was added thereto. After stirring at 110° C. for 25 hours, 3.87 g of ultrapure water was added for dilution. After stirring at 90° C. for 5 hours, the reaction mixture was left to cool and subjected to filtration by means of a pressure filter (filter paper: PF040, manufactured by Advantec Toyo Kaisha, Ltd.) to obtain 31.9 g of liquid composition S-1 having 13.5 mass % of the polymer H-1 dispersed in the mixed solvent. The viscosity at 25° C. at a shear rate of 76.6 s.sup.−1 was measured by means of an E-type viscometer, and it was 167 mPa.Math.s.

Ex. 6-2

(46) 20.0 g of liquid composition S-3 having 10 mass % of the polymer H-3 dispersed in the mixed solvent was obtained in the same manner as in Ex. 6-1, except that 2.0 g of the polymer H-3, 9.0 g of ethanol and 9.0 g of water were used.

Ex. 7

Ex. 7-1

(47) 20 g of a membrane of the polymer H′-1 being cut into small pieces and 56.9 g of a mixed solvent of ethanol/water (60/40 (mass ratio)) were added in an autoclave (internal capacity 200 mL, made of glass), and the autoclave was heated with stirring. After stirring at 115° C. for 16 hours, the autoclave was left to cool, followed by filtration by means of a pressure filter (filter paper: PF040, manufactured by Advantec Toyo Kaisha, Ltd.) to obtain 76.5 g of liquid composition S′-1 having 26.0 mass % of the polymer H′-1 dispersed in the mixed solvent. The viscosity at 25° C. at a shear rate of 76.6 s.sup.−1 was measured by means of an E-type viscometer, and it was 357 mPa.Math.s.

Ex. 8

Ex. 8-1 and Ex. 8-2

(48) A polymer electrolyte membrane was obtained by using the liquid composition S-1 or the liquid composition S-3 by the following method.

(49) A film was formed by applying the liquid composition on a 100 μm sheet made of an ethylene/tetrafluoroethylene copolymer by means of a die coater, followed by drying at 80° C. for 15 minutes and heat treatment at 185° C. for 30 minutes to obtain a polymer electrolyte membrane made of the polymer H (thickness: 25 μm). Results are shown in Table 5.

Ex. 9

Ex. 9-1

(50) A polymer electrolyte membrane made of the polymer H′-1 (thickness: 25 μm) was obtained in the same manner as in Ex. 8-1, except that the liquid composition S′-1 was used, and the heat treatment was carried out at a temperature of 160° C. for 30 minutes. Results are shown in Table 5.

(51) TABLE-US-00005 TABLE 5 Ex. Ex. 8-1 Ex. 8-2 Ex. 9-1 Polymer H H-1 H-2 H′-1 Used liquid composition S-1 S-3 S′-1 Softening temperature [° C.] 151 145 99 Conductivity [S/cm] 0.132 0.197 0.050 Moisture content [%] 152 At least 400 49

Ex. 10

Ex. 10-1

(52) 7.25 g of potassium fluoride and 26.6 mL of acetonitrile were charged in a 100 mL four-necked flask provided with a stirrer, a condenser, a thermometer and a dropping funnel. The flask was cooled in an ice bath, and 20.5 g of the reaction liquid obtained in Ex. 1-4 was dropwise added by means of a plastic syringe, while maintaining the internal temperature at from 0 to 10° C. by stirring. Intense heat generation was observed, and 15 minutes was spent for the dropwise addition. After completion of the dropwise addition, the ice bath was changed to a water bath, and the reaction was carried out at from 15 to 20° C. for 1 hour. The flask was cooled in an ice bath again, and 16.0 g of hexafluoropropylene oxide was gas-fed from a 1 L metal container, while maintaining the temperature of the reaction liquid at from 0 to 10° C. After completion of the feeding, the ice bath was changed to a water bath, and the reaction was carried out at from 20 to 25° C. for 48 hours. By-products were removed from the reaction liquid by suction filtration to recover a crude liquid. The solid removed by filtration was washed with an appropriate amount of acetonitrile, and the wash was mixed with the crude liquid. 57.4 g of the crude liquid was quantitatively analyzed by gas chromatography (GC), and it was confirmed that 1.0 mass % of the compound 8b-1 and 4.9 mass % of the compound 8a-1 were contained. The reaction yield of the compound 8b-1 on the compound 5-1 basis was 9.0%, and the reaction yield of the compound 8a-1 was 37.6%.

(53) ##STR00034##

(54) NMR spectrum of compound 8a-1; .sup.19F-NMR: −145.5 ppm (—CF.sub.2—CF(CF.sub.3)—O—, 1F), −138.0 ppm (—O—CF(CF.sub.2—SO.sub.2F).sub.2, 1F), −131.0 ppm (FOC—CF(CF.sub.3)—O—, 1F), −103.1 ppm (—CF.sub.2—SO.sub.2F, 4F), −82.0 ppm (FOC—CF(CF.sub.3)—O—, 3F), −82.0 ppm (—O—CF.sub.2—CF(CF.sub.3)—, 2F), −80.5 ppm (—CF.sub.2—CF(CF.sub.3)—O—, 3F),27.0 ppm (COF, 1F), 46.4 ppm (—SO.sub.2F, 2F).

(55) NMR spectrum of compound 8b-1;

(56) .sup.19F-NMR: −138.0 ppm (—O—CF(CF.sub.2—SO.sub.2F).sub.2, 1F), −131.0 ppm (FOC—CF(CF.sub.3)—O—,1F), −103.1 ppm (—CF.sub.2—SO.sub.2F, 4F), −82.0 ppm (FOC—CF(CF.sub.3)—O—, 3F), 27.0 ppm (COF, 1F), 46.4 ppm (—SO.sub.2F, 2F).

Ex. 10-2

(57) A fluidized-bed reactor having a length of 300 mm was produced by using a stainless steel tube having an inner diameter of 11.0 mm. 28 g of glass beads having an average diameter of 150 μm were packed in the fluidized-bed reactor, nitrogen gas was used as fluidization gas, and a metering pump was used to continuously supply starting materials. Outlet gas was collected by means of a trap tube with dry ice and acetone. 4.2 g of the reaction crude liquid in Ex. 10-1 was supplied to the fluidized-bed reactor over 1.5 hours so that the reaction crude liquid in Ex. 10-1/nitrogen gas=5/95 (molar ratio), while maintaining the reaction temperature in the fluidized bed reactor at 325° C. After completion of the reaction, 1.5 g of a crude liquid was obtained from the trap. The crude liquid was quantitatively analyzed by GC, and it was confirmed that 4.1 mass % of the compound 10-1 and 2.6 mass % of the compound 9-1 were contained. The reaction yield of the compound 9-1 on the compound 8a-1 basis was 6.8%, and the reaction yield of the compound 10-1 on the compound 8b-1 basis was 7.2%.

(58) ##STR00035##

(59) NMR spectrum of compound 9-1; .sup.19F-NMR: −145.5 ppm (—CF.sub.2—CF(CF.sub.3)—O—, 1F), −132.4 ppm (—O—CF(CF.sub.2—SO.sub.2F).sub.2, 1F), −136.0 ppm (CF.sub.2═CF—O—, 1F), −122.0 ppm (CF.sub.2═CF—O—, 1F), −114.0 ppm (CF.sub.2═CF—O—, 1F), −103.1 ppm (—CF.sub.2—SO.sub.2F, 4F), −82.0 ppm (—O—CF.sub.2—CF(CF.sub.3)—, 2F), −80.5 ppm (—CF.sub.2—CF(CF.sub.3)—O—, 3F), 46.4 ppm (—SO.sub.2F, 2F).

(60) NMR spectrum of compound 10-1; .sup.19F-NMR: −142.0 ppm (—O—CF(CF.sub.2—SO.sub.2F).sub.2, 1F), −136.0 ppm (CF.sub.2═CF—O—, 1F), −122.0 ppm (CF.sub.2═CF—O—, 1F), −114.0 ppm (CF.sub.2═CF—O—, 1F), −103.1 ppm (—CF.sub.2—SO.sub.2F, 4F), 46.4 ppm (—SO.sub.2F, 2F).

Ex. 11

(61) 80.7 g of the compound 9-1 and 9.1 mg of IPP are added in an autoclave (internal capacity 100 mL, made of stainless steel), followed by cooling and deaeration by liquid nitrogen. The internal temperature is raised to 40° C., and TFE is introduced in the autoclave to maintain the pressure at 0.55 MPaG (gage pressure). TFE is continuously added while maintaining the temperature and the pressure so that the pressure will be constant at 0.55 MPaG. After 7 hours, when the amount of added TFE reaches 2.7 g, the autoclave is cooled to terminate the polymerization, and gas in the system is purged. The reaction liquid is diluted with HFC-52-13p, and HFE-347pc-f is added to aggregate a polymer, followed by filtration. Then, an operation of stirring the polymer in HFC-52-13p and aggregating the polymer with HFE-347pc-f again is repeated twice, followed by drying under reduced pressure at 120° C. overnight to obtain 6.1 g of polymer F-6 which is a copolymer of TFE and the compound 9-1.

(62) The proportion of respective units constituting the polymer F-6 is obtained by .sup.19F-NMR, whereupon units based on TFE/units based on the compound 9-1=81.7/18.3 (molar ratio). The polymer F-6 has TO value of 296° C. The polymer F-6 has an ion exchange capacity of 2.0 (meq/g dry resin).

Ex. 12

(63) 49.6 g of the compound 9-1 is charged in an autoclave (internal capacity of 100 mL, made of stainless steel) under reduced pressure with cooling with ice water, followed by deaeration, and then 14.9 g of PDD is charged. After raising the temperature to 24° C., 0.1 MPa of nitrogen gas is introduced. After confirming no change in the pressure, 2.10 g of TFE is charged so that the total pressure will be 0.2 MPa (gage pressure). 11.7 mg of PFB dissolved in 0.39 g of HFC-52-13p is added under elevated pressure with nitrogen gas, and then the supply line is washed with 1.5 g of HFC-52-13p. While decreasing the rotational rate of stirring during the reaction from 100 rpm to 50 rpm so that ΔT between the jacket and the internal temperature will be minimum at the internal temperature of 24° C., after 12 hours from the initiation of the polymerization, gas in the system is purged to be replaced with nitrogen. The set temperature of the jacket is set to 24° C., the rotational rate of stirring is set to 5 rpm, and the pressure in the autoclave is gradually reduced to initiate distillation of a mixed liquid of unreacted PDD and the solvent. The set temperature of the jacket is gradually raised to 28° C., and 6.25 g of a distillate is obtained by a cold trap of a mixed liquid of HFC-225cb and dry ice after 2 hours. After stopping the distillation, the contents in the autoclave are diluted with 90 g of HFC-52-13p, followed by stirring at 20 rpm for 16 hours. A polymer solution at 25° C. discharged from the autoclave is added to a mixed liquid of 250 g of HFC-52-13p and 62.5 g of methanol at 20° C. to form particles. After stirring for 30 minutes, 170 g of a part of the polymer particles dispersion is taken out, and 55 g of methanol is added to the polymer particles dispersion. After stirring for 30 minutes, filtration is carried out. Then, washing is carried out by stirring and filtration with a mixed liquid of 50 g of HFC-52-13p and 21 g of methanol. After vacuum drying at 80° C. for 16 hours, vacuum drying at 240° C. is carried out for 16 hours to obtain 13.2 g of the polymer F-7.

(64) The proportion of respective units constituting the polymer F-7 is obtained by .sup.19F-NMR, and it will be units based on TFE/units based on the compound 9-1/units based on PDD=14.7/18.0/67.3 (molar ratio). The polymer F-7 has TQ value of 272° C. The polymer F-7 has an ion exchange capacity of 1.23 (meq/g dry resin).

Ex. 13

(65) 66.0 g of the compound 9-1, 25.9 g of PMVE and 2.03 g of HFC-52-13p are charged in an autoclave (internal capacity of 100 mL, made of stainless steel), followed by cooling and deaeration by liquid nitrogen. After raising the temperature to 40° C., TFE is charged until the pressure reaches 0.80 MPa (gage pressure). After confirming no change in the pressure, from a supply line attached to the autoclave, 0.28 g of a

(66) HFC-52-13p solution having 30.86 mg of IPP dissolved therein is added under elevated pressure with nitrogen gas, and then 1.0 g of HFC-52-13p is added to wash the supply line. While maintaining the temperature and the pressure at constant, TFE is continuously supplied to carry out polymerization. After 9.5 hours from the initiation of the polymerization, the autoclave is cooled to terminate the polymerization, and gas in the system is purged to obtain a solution of a polymer. 46.3 g of HFC-52-13p is added to the solution of the polymer and mixed. The temperature of the polymer solution is 25° C. The polymer solution is added to 216.3 g of HFE-347pc-f of −20° C. to aggregate the polymer, and particles are thereby formed. A liquid containing the particles of the polymer is filtered. 62.5 g of HFE-347pc-f is added to the obtained particles of the polymer, followed by stirring and then washing by filtration. The washing operation is carried out twice. The obtained particles of the polymer are dried under reduced pressure at 140° C. for 16 hours to obtain 6.5 g of polymer F-8.

(67) The proportion of the respective units constituting the polymer F-8 is obtained by .sup.19F-NMR, whereupon units based on TFE/units based on the compound 9-1/units based on PMVE=69.2/13.4/17.4 (molar ratio). The polymer F-8 has TQ value of 255° C. The polymer F-8 has an ion exchange capacity of 1.54 (meq/g dry resin).

INDUSTRIAL APPLICABILITY

(68) The fluorosulfonyl group-containing monomer of the present invention is useful as a starting material for a polymer, etc. to be contained in a catalyst layer or a polymer electrolyte membrane for a membrane/electrode assembly for a polymer electrolyte fuel cell or a membrane/electrode assembly for polymer electrolyte water electrolysis, a cation exchange membrane to be used for alkali chloride electrolysis, water electrolysis or electrodialysis, a diaphragm for a redox flow secondary cell, an ion exchange membrane for an electrochemical hydrogen pump, etc.

(69) This application is a continuation of PCT Application No. PCT/JP2018/032433, filed on Aug. 31, 2018, which is based upon and claims the benefit of priority from Japanese Patent Application No. 2017-168659 filed on Sep. 1, 2017, Japanese Patent Application No. 2018-091756 filed on May 10, 2018 and Japanese Patent Application No. 2018-091757 filed on May 10, 2018. The contents of those applications are incorporated herein by reference in their entireties.