Allyl group-containing fluoroalkylsulfonamide and method for producing same, fluoroalkylsulfonimide salt compound, polymer thereof, and method for producing the same

Abstract

To provide an allyl group-containing fluoroalkylsulfonamide compound capable of being transformed into a fluoroalkylsulfonimide salt compound, a convenient method for production thereof, a fluoroalkylsulfonimide salt compound, and a polymer thereof.SOLUTION: A method for producing a polymer is provided, wherein an allyl bromide compound is reacted with a vinyl group-substituted fluoroalkyl cyclic sulfonimide compound in the presence of a radical initiator; subsequently, an allyl group-containing fluoroalkylsulfonamide compound is produced by hydrolysis; further, the compound is transformed into a fluoroalkylsulfonimide salt compound, and such a fluoroalkylsulfonimide compound is polymerized.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an allyl-containing fluoroalkylsulfonamide and a method for producing the same, a fluoroalkylsulfonimide salt compound obtained by converting the allyl-containing fluoroalkylsulfonamide, a polymer obtained by polymerizing the fluoroalkylsulfonimide salt compound, and a method for producing the same. [Background technology]

[0002] Traditionally, organic electrolytes have been used as the electrolyte for lithium-ion batteries (LIBs). However, leakage and organic solvent ignition pose significant safety concerns, spurring the development of organic-solvent-free solid electrolytes. While inorganic solid electrolytes have demonstrated high electrical conductivity, their brittleness and hardness can lead to delamination from the electrode interface, resulting in reduced battery performance. Furthermore, their instability makes them difficult to handle, and other issues remain to be resolved. On the other hand, solid polymer electrolytes (SPEs), which are organic solid electrolytes, have the potential to achieve flexibility, stability, and high electrical conductivity. In particular, single lithium-ion conductors (SLICs), which do not exhibit electrolyte concentration gradients or cell polarization and thus are less susceptible to degradation in battery performance, are promising. In addition to using single lithium-ion conductors as solids, they can also be dissolved in liquid solvents. Compared to organic solid electrolytes, they offer higher conductivity. Furthermore, similar to solid electrolytes, they offer the potential for high cation transference numbers due to the controllable anion movement. However, due to the close ion spacing, counterion condensation is likely to occur, and they generally suffer from poor ionic dissociation and solubility.

[0003] Sulfonimide compounds are useful as electrolytes for lithium secondary batteries due to their excellent ionic conductivity, thermal stability, and chemical stability, and sulfonimide polymers have been investigated as SLICs. While sulfonimide compounds and their polymers have been synthesized, their synthesis is difficult, and only compounds and polymers with limited structures have been obtained. Non-Patent Document 1 describes two imide salt compounds substituted with fluoroalkyl sulfones: LiPBSI (lithium polyperfluorobutylene-1,4-bis-sulfonylimide) and LiPHSI (lithium polyperfluorohexylene-1,4-bis-sulfonylimide), which has a carbon chain two carbon atoms longer. However, these imide salts substituted with two fluoroalkyl sulfones are limited to very simple compounds. [ka]

[0004] As described above, sulfonimide salt compounds are useful materials as electrolytes for lithium secondary batteries. However, the fluoroalkyl sulfone-substituted imide salts that have been obtained to date are limited to those with very simple structures, which has limited the ability to investigate performance aspects such as the ionic conductivity of ionic conductors (polymers) and functional variations. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Lu, N.; Ho, YM; Fan, CW; Wang, FM; Lee, JT, Solid State Ionics 2007, 178, 347-353 Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above circumstances, an object of the present invention is to provide a fluoroalkylsulfonamide compound having an allyl group that can be converted into a fluoroalkylsulfonimide salt compound, and a simple method for producing the same. Another object is to provide a fluoroalkylsulfonamide compound having an allyl group by converting it to a fluoroalkylsulfonimide salt compound. A further object is to provide a polymer having a fluoroalkylsulfonimide anion moiety by polymerizing the fluoroalkylsulfonimide salt compound, and a method for producing the polymer. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems and have found that a fluoroalkylsulfonamide compound having an allyl group can be obtained by reacting a vinyl-substituted fluoroalkyl cyclic sulfonimide with a radical initiator and allyl bromide and then carrying out hydrolysis, thereby completing the present invention.

[0008] That is, the present invention relates to the following: [1] A method for producing a fluoroalkylsulfonamide compound having an allyl group, by reacting a vinyl-substituted fluoroalkyl cyclic sulfonimide compound with an allyl bromide compound in the presence of a radical initiator, followed by hydrolysis. [2] The method according to [1], wherein the vinyl-substituted fluoroalkyl cyclic sulfonimide compound is a compound represented by the following formula (1): [ka] (In the formula, Ar represents an aromatic group, R represents H or F, and at least one of R is F.) [3] The method according to [1], wherein the allyl bromide compound is a compound represented by the following formula (2): [ka] (In the formula, R 1 represents H, a lower alkyl group, or an ester group, and R2 and R 3 each independently represents H or a lower alkyl group. [4] A fluoroalkylsulfonamide compound having an allyl group represented by the following formula (3): [ka] (In the formula, R 1 , R 2 and R 3 is R in Equation (2) 1 , R 2 and R 3 The same as above.) [5] A method for producing a fluoroalkylsulfonimide salt compound by further converting a fluoroalkylsulfonamide compound having an allyl group in the production method according to [1]. [6] A fluoroalkylsulfonimide salt compound represented by the following formula (7): [ka] (In the formula, m represents an integer of 1 to 6.) [7] In the production method according to [5], a method for producing a polymer having a fluoroalkylsulfonimide anion moiety is provided, which is obtained by polymerizing a fluoroalkylsulfonimide salt compound or polymerizing a fluoroalkylsulfonimide salt compound and a dithiol compound. [8] A polymer having a fluoroalkylsulfonimide anion moiety represented by the following formula (8): [ka] (In the formula, m represents an integer of 1 to 6, and n represents polymerization.) [9] A polymer having a fluoroalkylsulfonimide anion moiety represented by the following formula (9): [ka] (In the formula, m represents an integer of 1 to 6, and n represents polymerization.) [Effects of the Invention]

[0009] According to the production method of the present invention, a fluoroalkylsulfonamide compound having an allyl group can be produced by a simple method. Furthermore, the fluoroalkylsulfonamide compound having an allyl group can be converted to a fluoroalkylsulfonimide salt compound. Furthermore, the fluoroalkylsulfonimide chloride can be converted to a polymer by polymerization using the terminal allyl group as a foothold. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a graph showing the effect of solvent on the conductivity versus temperature correlation of a polymer of the present invention. [Figure 2] 1 is a graph showing the correlation between conductivity and temperature for polymers of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention relates to a method for producing a fluoroalkylsulfonamide compound having an allyl group by reacting a vinyl-substituted fluoroalkyl cyclic sulfonimide compound with an allyl bromide compound in the presence of a radical initiator, followed by hydrolysis, as shown in the reaction scheme exemplified below. [ka]

[0012] The vinyl-substituted fluoroalkyl cyclic sulfonimide compound used in the production method of the present invention is not particularly limited as long as it is a vinyl-substituted fluoroalkyl cyclic sulfonyl imide compound, but a vinyl-substituted perfluoro cyclic sulfonyl imide compound represented by the following formula (1) is preferably used. [ka] In formula (1), Ar represents an aromatic group, and examples of the aromatic group include a phenyl group and a naphthyl group, and preferably a phenyl group. The aromatic group may have a substituent, and examples of the substituent include a halogen, a lower alkyl group, and an aromatic group. In formula (1), R represents H or F, and at least one of R is F. Perfluoro compounds in which all R are F are subject to stricter environmental regulations due to their high stability, and it is desirable to use not only perfluoro compounds but also partially substituted fluorine compounds from the standpoint of environmental regulations.

[0013] The radical initiator used in the production method of the present invention is not particularly limited, but a thermal polymerization initiator is preferred, and an azo polymerization initiator such as V-601 is particularly preferred. When an azo polymerization initiator such as V-601 is used, it is desirable to use it in an amount of about 0.2 equivalents relative to the substrate.

[0014] The allyl bromide compound used in the production method of the present invention is not particularly limited as long as it is a bromine compound having an allyl group, but an allyl bromide compound represented by the following formula (2) is preferred. [ka] In formula (2), R 1 represents H, a lower alkyl group, or an ester group, and R 2 and R 3 each independently represents H or a lower alkyl group. When the compound represented by formula (2) is used as the allyl bromide compound, the yield can be increased by using 3 or more equivalents relative to the substrate.

[0015] In the method for producing a fluoroalkylsulfonamide compound having an allyl group of the present invention, the reaction of a vinyl-substituted fluoroalkyl cyclic sulfonimide compound with an allyl bromide compound in the presence of a radical initiator is carried out in an organic solvent. The type of organic solvent is not particularly limited, but a halogenated organic solvent such as 1,2-dichloroethane is preferably used. The reaction temperature and reaction time can be appropriately set depending on the type and amount of the radical initiator used. For example, when the azo-based polymerization initiator V-601 is used as the radical initiator in an amount of 0.2 equivalents relative to the substrate, the reaction temperature is 90°C and the reaction time is approximately 3 hours.

[0016] The method for producing a fluoroalkyl sulfonamide compound having an allyl group of the present invention involves reacting a vinyl-substituted fluoroalkyl cyclic sulfonimide compound with an allyl bromide compound in the presence of a radical initiator, followed by hydrolysis. The hydrolysis method and conditions are not particularly limited, and the hydrolysis can be carried out by a conventional method. For example, in the examples, Nafion and water were used, and hydrolysis was carried out at 70°C for 1 hour using tetrahydrofuran as a solvent.

[0017] The method for producing a fluoroalkylsulfonamide compound having an allyl group of the present invention can produce a fluoroalkylsulfonamide compound having an allyl group represented by the following formula (3): 1 , R 2 and R 3 is R in Equation (2) 1 , R 2 and R 3 is the same as [ka]

[0018] The fluoroalkyl sulfonamide compound having an allyl group obtained by the production method of the present invention can be further converted into a fluoroalkyl sulfonimide salt compound. The conversion method is not particularly limited, but the conversion can be performed using any one selected from fluoroalkanesulfonic acid anhydride, fluoroalkanesulfonic acid chloride, fluoroalkanesulfonic acid fluoride, fluoroalkanedisulfonic acid anhydride, fluoroalkanedisulfonic acid chloride, and fluoroalkanedisulfonic acid fluoride and a base. Furthermore, the fluoroalkyl sulfonamide compound having an allyl group obtained by the production method of the present invention can be converted into a fluoroalkyl sulfonimide salt compound by reacting it with a fluoroalkyl disulfone compound or a fluoroalkyl trisulfone compound.

[0019] Examples of fluoroalkanesulfonic acid anhydrides include trifluoromethanesulfonic acid anhydride, pentafluoroethanesulfonic acid anhydride, and heptafluoropropanesulfonic acid anhydride. Examples of fluoroalkanesulfonic acid chlorides include trifluoromethanesulfonic acid chloride, pentafluoroethanesulfonic acid chloride, and heptafluoropropanesulfonic acid chloride. Examples of fluoroalkanesulfonic acid fluorides include trifluoromethanesulfonic acid fluoride, pentafluoroethanesulfonic acid fluoride, and heptafluoropropanesulfonic acid fluoride. Examples of fluoroalkanedisulfonic acid anhydrides include difluoromethanedisulfonic acid anhydride, tetrafluoroethanedisulfonic acid anhydride, hexafluoropropanesulfonic acid anhydride, and tetrafluoroethanedisulfonic acid anhydride. Examples of the fluoroalkanedisulfonic acid chloride include difluoromethanedisulfonic acid chloride, tetrafluoroethanedisulfonic acid chloride, hexafluoropropanedisulfonic acid chloride, octafluorobutanedisulfonic acid chloride, decafluoropentanedisulfonic acid chloride, and undecafluorohexanedisulfonic acid chloride. Examples of the fluoroalkanedisulfonic acid fluoride include difluoromethanedisulfonic acid fluoride, tetrafluoroethanedisulfonic acid fluoride, hexafluoropropanedisulfonic acid fluoride, octafluorobutanedisulfonic acid fluoride, decafluoropentanedisulfonic acid fluoride, and dodecafluorohexanedisulfonic acid fluoride. The chemical formulae of trifluoromethanesulfonic anhydride (formula (4)) as the fluoroalkanesulfonic anhydride, trifluoromethanesulfonic acid chloride (formula (5)) as the fluoroalkanesulfonic acid chloride, and trifluoromethanesulfonic acid fluoride (formula (6)) as the fluoroalkanesulfonic acid fluoride are shown below. [ka]

[0020] Examples of the base used in the method for converting to a fluoroalkylsulfonimide salt compound include organic bases such as triethylamine, diisopropylethylamine, pyridine, 2,6-lutidine, 2,6-dichloropyridine, 2,4,6-trimethylpyridine, 2,4,6-tri-tert-butylpyridine, 2,6-di-tert-butyl-4-methylpyridine, 2,6-di-tert-butylpyridine, 2,4,6-tri-tert-butylpyrimidine, butyllithium, and lithium diisopropylamine; and inorganic bases such as potassium carbonate, sodium carbonate, lithium hydride, sodium hydride, potassium hydride, lithium carbonate, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, and potassium hydroxide.

[0021] According to the method for producing a fluoroalkylsulfonimide salt compound of the present invention, a fluoroalkylsulfonimide salt compound represented by the following formula (7) can be produced. [ka] (In the formula, m represents an integer of 1 to 6.)

[0022] The fluoroalkylsulfonimide salt compound obtained by the production method of the present invention can be further polymerized to produce a polymer having a fluoroalkylsulfonimide anion moiety represented by the following formula (8). [ka] (In the formula, m represents an integer of 1 to 6, and n represents polymerization.) The polymerization can be carried out using metathesis polymerization utilizing the terminal allyl group of the fluoroalkylsulfonimide salt compound, and a second-generation Grubbs catalyst can be used. The metathesis polymerization can be carried out according to a standard method, and the solvent used is not particularly limited as long as it dissolves the fluoroalkylsulfonimide salt compound, and examples include ethylene glycol, dimethyl carbonate, and tetrahydrofuran. The polymerization temperature is in the range of 0 to 150°C, for example, 45 to 90°C, and the polymerization pressure is approximately 1 atmosphere.

[0023] Furthermore, the fluoroalkylsulfonimide salt compound obtained by the production method of the present invention can be subjected to a thiol salt reaction using a dithiol compound and a radical polymerization initiator to produce a polymer having a fluoroalkylsulfonimide anion moiety, as exemplified by the following formula (9), which is made of a monomer unit having a dithiol group bonded to the fluoroalkylsulfonimide anion moiety. [ka] (In the formula, m represents an integer of 1 to 6, and n represents polymerization.) The dithiol compound to be used is not particularly limited, and examples thereof include 1,2-ethanedithiol, 1,2-propanediol, 1,3-propanedithiol, 1,2-butanedithiol, 1,4-butanediol, 1,5-pentanedithiol, 2,3-butanediol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanediol, 3,6-dioxa-1,8-octanedithiol, bis(2-mercaptoethyl)ether, hexa(ethylene glycol)dithiol, 3,7-dithia-1,9-nonanedithiol, PEG, Examples include 2,3-dimercapto-1-propanol, meso-2,3-dimercaptosuccinic acid, dithioerythritol, ethylene glycol bisthioglycolate, 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, benzene 1,2-dithiol, benzene 1,3-dithiol, benzene 1,4-dithiol, 4,4'-thiodibenzenethiol, 4,4-biphenyldithiol, and 1,5-dimercaptonaphthalene. The radical polymerization initiator used is not particularly limited, and may be any initiator that generates radicals when exposed to light or heat. It can be suitably used as a precursor to sulfonimide polymers having a variety of structures. [Example]

[0024] The present invention will be described in more detail below using examples, but the present invention is not limited to the scope of these examples. [Example 1]

[0025] In Example 1, the compound represented by formula (1) used as the starting material was a compound in which Ar is a phenyl group, and the allyl bromide compound represented by formula (2) was a compound in which R 1 is an ethyl ester group, and R 2 and R 3The relationship between the equivalent of allyl bromide compound used in the reaction and the yield of fluoroalkylsulfonamide compound having an allyl group was investigated by reacting a compound in which both are H according to the reaction conditions described in the following reaction formula.

[0026] [ka]

[0027] The results of Example 1 are shown in Table 1. [Table 1] The yield is 1 The values ​​in parentheses indicate the isolated yield. [Example 2]

[0028] In Example 2, the amount of the allyl bromide compound was fixed at 5 equivalents, and the other conditions were the same as in Example 1, as shown in the following reaction formula, to obtain R 1 (represented as R in the following reaction formula) on the yield of the fluoroalkylsulfonamide compound having an allyl group was examined.

[0029] [ka]

[0030] The results of Example 2 are shown in Table 2. [Table 2] The yield is 1 The values ​​in parentheses indicate the isolated yield. [Example 3]

[0031] An allyl-containing fluoroalkylsulfonamide compound (1,1,2,2,3,3-hexafluorohex-5-ene-1-sulfonamide) represented by the following formula (8) was synthesized. [ka]

[0032] 4,4,5,5,6,6-hexafluoro-2-(1-phenylvinyl)-1,3,2-dithiazinane 1,1,3,3-tetraoxide (199.5 mg, 0.5 mmol, 1 equiv) and V-601 (23.8 mg, 0.1 mmol, 0.2 equiv) were added to a 30 mL two-neck flask and the atmosphere was purged with nitrogen. Next, CHClCHCl (2 mL) and allyl bromide (306.5 mg, 2.53 mmol, 5.06 equiv) were added and the mixture was heated and stirred at 90 °C for 3 h. After stirring, the mixture was concentrated using an evaporator and vacuum pump. Next, Nafion (90 mg) was added and the atmosphere was purged with nitrogen. Next, THF (2 mL) and HO (540.7 mg, 30.01 mmol, 60.02 equiv) were added and the mixture was stirred at 70 °C for 1 h. The reaction mixture was transferred to a 50 mL eggplant-shaped flask and concentrated using an evaporator and vacuum pump to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 1,1,2,2,3,3-hexafluorohex-5-ene-1-sulfonamide (101.5 mg, 75% yield). 1,1,2,2,3,3-hexafluorohex-5-ene-1-sulfonamide 1H-NMR (500 MHz,CHLOROFORM-D) δ 5.85-5.77 (m, 1H), 5.37-5.32 (m, 2H), 5.17 (s, 2H), 2.87 (td, J= 18.3, 7.0 Hz, 2H); 19F-NMR (470 MHz, CHLOROFORM-D) δ -112.0 (t, J = 12.0 Hz,2F), -112.7--112.8 (m, 2F), -121.2 (m, 2F). [Example 4]

[0033] An allyl group-containing fluoroalkylsulfonamide compound (ethyl 4,4,5,5,6,6-hexafluoro-2-methylene-6-sulfamoylhexanoate) represented by the following formula (9) was synthesized. [ka]

[0034] 4,4,5,5,6,6-hexafluoro-2-(1-phenylvinyl)-1,3,2-dithiazinane 1,1,3,3-tetraoxide (199.2 mg, 0.5 mmol, 1 equiv) and V-601 (23.5 mg, 0.1 mmol, 0.2 equiv) were added to a 30 mL two-neck flask and purged with nitrogen. Next, CHClCHCl (2 mL) and Ethyl 2-(Bromomethyl)acrylate (488 mg, 2.53 mmol, 5.06 equiv) were added and heated and stirred at 90 °C for 3 h. After stirring, the mixture was concentrated using an evaporator and vacuum pump, and Nafion (89 mg) was added and purged with nitrogen. Next, THF (2 mL) and HO (543.2 mg, 30.14 mmol, 60.28 equiv) were added and stirred at 70 °C for 1 h. The reaction mixture was transferred to a 50 mL eggplant-shaped flask and concentrated using an evaporator and vacuum pump to obtain a crude product (510.7 mg). The crude product was purified by silica gel column chromatography to obtain 138.5 mg of ethyl 4,4,5,5,6,6-hexafluoro-2-methylene-6-sulfamoylhexanoate in a 72% yield. ethyl4,4,5,5,6,6-hexafluoro-2-methylene-6-sulfamoylhexanoate 1H-NMR (500 MHz,CHLOROFORM-D) δ 6.55 (s, 1H), 5.92 (s, 1H), 5.35 (s, 2H), 4.25(q, J = 7.1 Hz,2H), 3.21 (t, J = 18.5 Hz, 2H), 1.31 (t, J = 7.2 Hz, 3H); 19F-NMR(470 MHz,CHLOROFORM-D) δ -111.9--112.0 (m, 2F), -112.9--113.1 (m, 2F), -121.3--121.5 (m,2F); 19F-NMR (470 MHz, CHLOROFORM-D) δ -111.9--112.0 (m, 2F), -112.9--113.1 (m,2F), -121.3--121.5 (m, 2F); 13C{1H}{19F} NMR (126 MHz, CHLOROFORM-D)δ 166.2,132.6, 129.4, 116.8, 114.3, 111.1, 77.3, 77.0, 76.7, 61.7, 32.2, 13.9 [Example 5]

[0035] An allyl-containing fluoroalkylsulfonamide compound (1,1,2,2,3,3-hexafluoro-5-methylhex-5-ene-1-sulfonamide) represented by the following formula (10) was synthesized. [ka]

[0036] 4,4,5,5,6,6-hexafluoro-2-(1-phenylvinyl)-1,3,2-dithiazinane 1,1,3,3-tetraoxide (198.9 mg, 0.5 mmol, 1 equiv) and V-601 (27.1 mg, 0.12 mmol, 0.24 equiv) were added to a 10 mL two-neck flask and the atmosphere was purged with nitrogen. Next, CHClCHCl (2 mL) and methallyl bromide (337.9 mg, 2.5 mmol, 5 equiv) were added and stirred at 90 °C for 3 h. After stirring, the mixture was concentrated using an evaporator and vacuum pump, and Nafion (92.2 mg) was added and the atmosphere was purged with nitrogen. Next, THF (2 mL) and HO (538 mg, 29.86 mmol, 59.72 equiv) were added and the mixture was stirred at 70 °C for 1 h. The reaction mixture was transferred to a 20 mL eggplant-shaped flask and concentrated using an evaporator and vacuum pump to obtain the crude product. CHCl2CHCl2 (42.4 mg, 0.253 mmol) and PhCF3 (37 mg, 0.253 mmol) were added. The mixture was purified by silica gel column chromatography to obtain 1,1,2,2,3,3-hexafluoro-5-methylhex-5-ene-1-sulfonamide (103.3 mg, 72% yield). 1,1,2,2,3,3-hexafluoro-5-methylhex-5-ene-1-sulfonamide 1H-NMR (500 MHz,CHLOROFORM-D) δ 5.27 (s, 2H), 5.10 (t, J = 1.5 Hz, 1H), 4.97 (s, 1H), 2.80 (t,J = 19.3 Hz, 2H), 1.87 (s, 3H); 19F-NMR 13C{1H}{19F} NMR (126MHz, CHLOROFORM-D) δ 134.2, 118.9, 117.8, 114.4, 111.2, 38.5, 23.4. [Example 6]

[0037] A fluoroalkylsulfonamide compound having an allyl group (1,1,2,2,3,3-hexafluoro-5-bromohex-5-ene-1-sulfonamide) represented by the following formula (11) was synthesized. [ka]

[0038] 4,4,5,5,6,6-hexafluoro-2-(1-phenylvinyl)-1,3,2-dithiazinane 1,1,3,3-tetraoxide (195.4 mg, 0.49 mmol, 1 equiv) and V-601 (24 mg, 0.1 mmol, 0.2 equiv) were added to a 30 mL two-neck flask and the atmosphere was purged with nitrogen. Next, CHClCHCl (2 mL) and 2,3-Dibromopropene (497.7 mg, 2.49 mmol, 5.08 equiv) were added and stirred at 90 °C for 3 h. After stirring, the mixture was concentrated using an evaporator and vacuum pump, and Nafion (93.3 mg) was added and the atmosphere was purged with nitrogen. Next, THF (2 mL) and HO (541.5 mg, 30.05 mmol, 61.33 equiv) were added and the mixture was stirred at 70 °C for 1 h. The reaction mixture was transferred to a 50 mL round-bottom flask and concentrated using an evaporator and a vacuum pump to obtain a crude product (271.3 mg), which was then purified by column chromatography to obtain the desired product in 75% yield. 1H-NMR (500 MHz,CHLOROFORM-D) δ 5.92 (d, J = 1.9 Hz, 1H), 5.84 (d, J = 2.0 Hz, 1H), 5.24 (s,2H), 3.28 (t, J = 17.1 Hz, 2H) 19F-NMR (470 MHz,CHLOROFORM-D) δ -111.9--111.9 (m, 2F), -113.1--113.3 (m, 2F), -121.2--121.2 (m,2F) [Example 7]

[0039] According to the following reaction scheme, a fluoroalkylsulfonimide salt compound represented by the following formula (7) was synthesized using the fluoroalkylsulfonamide compound having an allyl group represented by formula (8) obtained in Example 3 above.

[0040] [ka]

[0041] 1,1,2,2,3,3-Hexafluorohex-5-ene-1-sulfonamide (1235.8 mg, 4.56 mmol, 2 equiv) and LiH (356.1 mg, 44.79 mmol, 19.64 equiv) were added to a 20 mL two-neck flask. Next, 1,1,2,2,3,3-Hexafluoropropane-1,3-disulfonyldifluoride (721.2 mg, 2.28 mmol, 1 equiv) dissolved in THF (8.4 mL) was added and the mixture was stirred at 60 °C for 16 h. After stirring, the precipitate was filtered through Celite, and the filtrate was concentrated using an evaporator and a vacuum pump to obtain the crude product (1481.2 mg). THF (8.4 mL) and LiH (362 mg, 45.53 mmol, 19.97 equiv) were added again, and the mixture was stirred at 60°C for 90 hours. After stirring, the precipitate was filtered through Celite, and the filtrate was concentrated using an evaporator and a vacuum pump to obtain the crude product (1267.7 mg). The obtained product was washed with chloroform to obtain 259 mg (0.312 mmol, 14%) of the desired product as a precipitate. 1H-NMR (500 MHz, ACETONE-D6)δ 5.87-5.81 (m, 2H), 5.39-5.29 (m, 4H), 3.00-2.91 (m, 4H) [Example 8]

[0042] According to the following reaction scheme, a polymer having a fluoroalkylsulfonimide anion moiety was synthesized using the fluoroalkylsulfonimide compound having an allyl group at its terminal and represented by formula (7) obtained in Example 7 above (referred to as C3 monomer in the following reaction scheme). [ka]

[0043] A 20 mL two-neck flask was charged with C3 monomer (327.9 mg, 0.4 mmol, 1 equiv) and Grubbs 2nd (3.7 mg, 0.004 mmol, 0.01 equiv). Propylene carbonate (2 mL) was then added in a glove box, and the mixture was stirred at 45 °C for 3 hours under vacuum (0.26 mmHg). After stirring, the reaction mixture was transferred to a 300 mL recovery flask, toluene (200 mL) was added, and the mixture was stirred for 18 hours. The toluene was then removed. This washing procedure was repeated. The mixture was concentrated using an evaporator and a vacuum pump to obtain the crude product (317.6 mg). The sample was then transferred to an NMR tube and subjected to NMR measurement. [Example 9]

[0044] A polymer bearing fluoroalkylsulfonimide anion moieties was synthesized using a fluoroalkylsulfonimide compound bearing an allyl group at its terminal according to the following reaction scheme. (In the following reaction scheme, the fluoroalkylsulfonimide compound bearing an allyl group at its terminal is referred to as C1 monomer, and the resulting polymer is referred to as polyanion C1.) [ka] C1 monomer (190.7 mg, 0.26 mmol, 1 equiv) and Grubbs 2nd (4.3 mg, 0.01 mmol, 0.04 equiv) were added to a 20 mL two-neck flask. Tetrahydrofuran (1.5 mL) was then added and the mixture was stirred at 45 °C for 3 hours. After stirring, the reaction mixture was transferred to a 50 mL recovery flask and concentrated using an evaporator and vacuum pump to obtain the crude product (183.9 mg). The sample was then transferred to an NMR tube and subjected to NMR measurement. [Example 10]

[0045] According to the following reaction formula, a polymer having a fluoroalkylsulfonimide anion moiety was synthesized using the fluoroalkylsulfonimide compound having an allyl group at its terminal, represented by formula (7) obtained in Example 7 above, and a dithiol compound. [ka] A 20 mL two-necked recovery flask was charged with a fluoroalkylsulfonimide compound (720.3 mg, 0.88 mmol, 1 equiv) bearing an allyl group at its terminal and azobisisobutyronitrile (AIBN: 29.6 mg, 0.18 mmol, 0.2 equiv) as a polymerization initiator. Next, PC (1.5 mL) and 3,6-dioxa-1,8-octanedithiol (163.2 mg, 0.9 mmol, 1.02 equiv) as a dithiol compound were added in a glove box. The mixture was stirred at 90 °C for 3 hours under vacuum (0.26 mmHg). After stirring, the reaction mixture was transferred to a 300 mL recovery flask, toluene (100 mL) was added, and the mixture was stirred for 18 hours. The toluene was then removed. This washing procedure was repeated. The mixture was concentrated using an evaporator and a vacuum pump to obtain polymer C (940 mg).The sample was then transferred to an NMR tube and subjected to NMR measurement. [Example 11]

[0046] The polymer obtained in Example 8 was dissolved in ethylene carbonate (EC) and dimethyl carbonate (DMC), and the correlation between conductivity and temperature was measured to determine the optimal ratio of ethylene carbonate (EC) to dimethyl carbonate (DMC) as a solvent. Measurements were performed by AC impedance analysis using a Biologic SP-150 at a voltage of 0.01 V and a frequency range of 1 MHz to 1 Hz. The results are shown in Figure 1. Figure 1 indicates that the optimal ratio of ethylene carbonate (EC) to dimethyl carbonate (DMC) is 1:3. In subsequent conductivity measurements, a solvent with an ethylene carbonate (EC) to dimethyl carbonate (DMC) ratio of 1:3 was used.

[0047] The polymer obtained in Example 8 (referred to as polyanion C3 in the tables below), the polymer obtained in Example 9 (referred to as polyanion C1 in the tables below), the fluoroalkylsulfonimide compound having an allyl group at the end used in Example 9 (referred to as monomer (C1) in the tables below), and the polymer obtained in Example 10 (referred to as polyanion C3-DMDO in the tables below) were dissolved in ethylene carbonate (EC) and dimethyl carbonate (DMC), and their conductivity was measured at each temperature. The measurement conditions were the same as those described above. The results are shown in Table 2, and the correlation between conductivity and temperature is shown as a graph in Figure 2. It was revealed that the polymers of the present invention having fluoroalkylsulfonimide anion moieties exhibit high conductivity. [Table 2] [Industrial Applicability]

[0048] By polymerizing the compounds obtained by this production method in various ways, they are expected to be used in a variety of applications, such as polymer electrolytes for lithium-ion batteries, separators, and coating agents for the negative electrodes of next-generation secondary batteries. In particular, the introduction of flexible or rigid spacers is expected to lead to the development of new main-chain single-ion conductors, as well as new main-chain single-ion conductors by introducing spacers designed for decomposition after use.

Claims

1. A method for producing a fluoroalkylsulfonamide compound having an allyl group, comprising reacting a vinyl-substituted fluoroalkyl cyclic sulfonimide compound with an allyl bromide compound in the presence of a radical initiator, followed by hydrolysis.

2. The method according to claim 1, wherein the vinyl-substituted fluoroalkyl cyclic sulfonimide compound is a compound represented by the following formula (1): 【Chemical 1】 (In the formula, Ar represents an aromatic group, R represents H or F, and at least one of R is F.)

3. The method according to claim 1, wherein the allyl bromide compound is a compound represented by the following formula (2): 【Chemistry 2】 (In the formula, R １ represents H, a lower alkyl group, or an ester group; R ２ and R ３ each independently represents H or a lower alkyl group.

4. A fluoroalkylsulfonamide compound having an allyl group represented by the following formula (3): 【Chemistry 3】 (In the formula, R １ , R ２ and R ３ is R in formula (2). １ , R ２ and R ３ is the same as

5. 2. A method for producing a fluoroalkylsulfonimide salt compound by further converting a fluoroalkylsulfonamide compound having an allyl group in the production method according to claim 1.

6. A fluoroalkylsulfonimide salt compound represented by the following formula (7): 【Chemistry 4】 (wherein m represents an integer of 1 to 6.)

7. 6. The method for producing a polymer having a fluoroalkylsulfonimide anion moiety according to claim 5, wherein the polymer is produced by polymerizing a fluoroalkylsulfonimide salt compound or by polymerizing a fluoroalkylsulfonimide salt compound and a dithiol compound.

8. A polymer having a fluoroalkylsulfonimide anion moiety represented by the following formula (8): 【Chemistry 5】 (In the formula, m represents an integer of 1 to 6, and n represents polymerization.)

9. A polymer having a fluoroalkylsulfonimide anion moiety represented by the following formula (9): 【Chemistry 6】 (In the formula, m represents an integer of 1 to 6, and n represents polymerization.)

Images