阅读说明：本技术 含有甲硅烷基醚的磺酸盐 (Sulfonic acid salts containing silyl ethers ) 是由 南条真佐人 增田现 于 2020-02-04 设计创作，主要内容包括：提供包含由下述式(1)表示的阴离子、和阳离子的含有甲硅烷基醚的磺酸盐。(式中,R～(1)～R～(4)各自独立地为碳原子数1～4的烷基。m为1～3的整数。n为2～8的整数。)(Provided is a silyl ether-containing sulfonate salt that contains an anion represented by the following formula (1) and a cation. (in the formula, R 1 ～R 4 Each independently is an alkyl group having 1 to 4 carbon atoms. m is an integer of 1 to 3. n is an integer of 2 to 8. ))

1. A silyl ether-containing sulfonate comprising a cation and an anion represented by the following formula (1),

[ solution 1]

In the formula, R¹～R⁴Each independently an alkyl group having 1 to 4 carbon atoms, m is an integer of 1 to 3, and n is an integer of 2 to 8.

2. The salt of claim 1, wherein R¹～R³Are the same group.

3. The salt of claim 2, wherein R¹～R³Is methyl.

4. The salt of claim 1, wherein R¹Is a reaction with R²And R³Different radicals R²And R³Are the same group.

5. The salt of claim 4, wherein R¹Is alkyl of 2-4 carbon atoms, R²And R³Is methyl.

6. The salt of any one of claims 1 to 5, wherein m is 1 or 2.

7. The salt of any one of claims 1-6, wherein R⁴Is methyl.

8. The salt of any one of claims 1 to 7, wherein n is 2 or 3.

9. A salt according to any one of claims 1 to 8, wherein the cation is an organic cation.

10. The salt of claim 9, wherein the cation is an organic cation comprising a phosphorus atom.

11. The salt of claim 9, wherein the cation is an organic cation containing a nitrogen atom.

12. The salt of any one of claims 1 to 11, which is an ionic liquid having a melting point below 100 ℃.

13. The salt of claim 12, which is an ionic liquid having a melting point below 25 ℃.

Technical Field

The present invention relates to silyl ether containing sulfonates.

Background

The ionic liquid is a salt having a melting point of 100 ℃ or lower and consisting of only ions. Various applications of ionic liquids have been studied based on their properties. Many of the ionic liquids known so far have a problem in terms of environmental load because anions contain halogen atoms such as fluorine atoms, and a halogen-free ionic liquid is desired.

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel salt which can be an ionic liquid containing no halogen atom.

Means for solving the problems

The present inventors have made extensive studies to achieve the above object, and as a result, have found that the above object can be achieved by a sulfonic acid salt having a silyl ether structure, and have completed the present invention.

Namely, the present invention provides the following silyl ether-containing sulfonic acid salt.

1. A silyl ether-containing sulfonate comprising an anion represented by the following formula (1) and a cation.

[ solution 1]

(in the formula, R¹～R⁴Each independently is an alkyl group having 1 to 4 carbon atoms. m is an integer of 1 to 3. n is an integer of 2 to 8. )

2.1 wherein R is¹～R³Are the same group.

3.2 wherein R is¹～R³Is methyl.

4.1 wherein R is¹Is a reaction with R²And R³Different radicals R²And R³Are the same group.

The salt of 5.4, wherein R¹Is alkyl of 2-4 carbon atoms, R²And R³Is methyl.

The salt according to any one of claims 1 to 5, wherein m is 1 or 2.

The salt according to any one of claims 1 to 6, wherein R⁴Is methyl.

The salt according to any one of claims 1 to 7, wherein n is 2 or 3.

The salt according to any one of claims 1 to 8, wherein the cation is an organic cation.

10.9, wherein the cation is an organic cation containing a phosphorus atom.

11.9, wherein the cation is an organic cation containing a nitrogen atom.

12.1 to 11, which is an ionic liquid having a melting point of 100 ℃ or lower.

13.12, which is an ionic liquid having a melting point below 25 ℃.

ADVANTAGEOUS EFFECTS OF INVENTION

The silyl ether-containing sulfonate of the present invention is an ionic liquid depending on the kind of cation, and does not contain a halogen, so that the environmental burden is small.

Drawings

FIG. 1 shows BDDP MeSilC prepared in example 2-1₂SO₃Is/are as follows¹H-NMR spectrum.

FIG. 2 is a BDDP MeSilC prepared in example 2-1₂SO₃DSC chart of (a).

FIG. 3 is a BHDP MeSilC prepared in example 2-2₂SO₃Is/are as follows¹H-NMR spectrum.

FIG. 4 is a BHDP MeSilC prepared in example 2-2₂SO₃DSC chart of (a).

FIG. 5 shows BDDP MeSilC prepared in examples 2-3₃SO₃Is/are as follows¹H-NMR spectrum.

FIG. 6 is a BDDP MeSilC prepared in examples 2-3₃SO₃DSC chart of (a).

FIG. 7 shows BHDP MeSilC prepared in examples 2-4₃SO₃Is/are as follows¹H-NMR spectrum.

FIG. 8 is a schematic view of an embodimentBHDP MeSilC prepared in examples 2-4₃SO₃DSC chart of (a).

FIG. 9 shows BDDP BuSilC prepared in examples 2-5₂SO₃Is/are as follows¹H-NMR spectrum.

FIG. 10 shows BDDP BuSilC prepared in examples 2-5₂SO₃DSC chart of (a).

FIG. 11 shows BHDP BuSilC prepared in examples 2-6₂SO₃Is/are as follows¹H-NMR spectrum.

FIG. 12 shows BHDP BuSilC prepared in examples 2-6₂SO₃DSC chart of (a).

FIG. 13 shows BDDP BuSilC prepared in examples 2-7₃SO₃Is/are as follows¹H-NMR spectrum.

FIG. 14 shows BDDP BuSilC prepared in examples 2-7₃SO₃DSC chart of (a).

FIG. 15 shows BHDP BuSilC prepared in examples 2-8₃SO₃Is/are as follows¹H-NMR spectrum.

FIG. 16 shows BHDP BuSilC prepared in examples 2-8₃SO₃DSC chart of (a).

FIG. 17 is BDDP Me (Me) prepared in examples 2-9₃SiO)₂SiC₂SO₃Is/are as follows¹H-NMR spectrum.

FIG. 18 is BDDP Me (Me) made in examples 2-9₃SiO)₂SiC₂SO₃DSC chart of (a).

FIG. 19 is BHDP Me (Me) prepared in examples 2-10₃SiO)₂SiC₂SO₃Is/are as follows¹H-NMR chart.

FIG. 20 is BHDP Me (Me) prepared in examples 2-10₃SiO)₂SiC₂SO₃DSC chart of (a).

FIG. 21 shows MEMP MeSilC prepared in examples 2-11₂SO₃Is/are as follows¹H-NMR spectrum.

FIG. 22 shows MEMP MeSilC prepared in examples 2-11₂SO₃DSC chart of (a).

Detailed Description

[ silyl ether-containing sulfonic acid salt ]

The silyl ether-containing sulfonate of the present invention contains an anion represented by the following formula (1) and a cation.

[ solution 2]

In the formula (1), R¹～R⁴Each independently is an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched and cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl and the like. Among these, as R¹～R³Preferably, the alkyl group has 1 to 4 carbon atoms.

R¹～R³Preferably, all are the same group, more preferably all are methyl or ethyl, and still more preferably all are methyl. Alternatively, R is also preferred¹Is a reaction with R²And R³Different radicals R²And R³Are the same group, in this case, R is more preferably¹Is alkyl of 2-4 carbon atoms, R²And R³Is methyl.

As R⁴The alkyl group is preferably a linear alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

In the formula (1), m is an integer of 1 to 3, preferably 1 or 2. n is an integer of 2 to 8, preferably 2 to 6, more preferably 2 or 3.

The cation contained in the silyl ether containing sulfonate of the present invention is not particularly limited, and a cation having a valence of 1 is preferable. The cation may be an inorganic cation or an organic cation, and is preferably an organic cation.

Examples of the inorganic cation include alkali metal ions such as sodium ion, potassium ion, and lithium ion, and metal ions such as magnesium ion, silver ion, zinc ion, and copper ion.

The organic cation is preferably an organic cation containing a phosphorus atom or an organic cation containing a nitrogen atom, and specifically, a quaternary phosphonium ion, a quaternary ammonium ion, an imidazolium ion, a pyridinium ion, a pyrrolidinium ion, a piperidinium ion, or the like is preferable.

As the organic cation containing a phosphorus atom, for example, a quaternary phosphonium ion represented by the following formula (2) is preferable.

[ solution 3]

In the formula (2), R¹¹Is an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be any of a straight chain, branched chain and cyclic, and specific examples thereof include, in addition to the alkyl groups having 1 to 8 carbon atoms, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-eicosyl group.

In the formula (2), R¹²Is alkyl with 1-20 carbon atoms or- (CH)₂)_kAlkoxyalkyl groups represented by-OR. k is 1 or 2. R is methyl or ethyl. The alkyl group having 1 to 20 carbon atoms includes the above alkyl groups. Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group. Among the above alkoxyalkyl groups, a methoxymethyl group or a methoxyethyl group is preferable.

In the quaternary phosphonium ion represented by the formula (2), R¹²Is composed of- (CH)₂)_kThe alkoxyalkyl group represented by-OR readily forms an ionic liquid. At R¹²In the case of alkyl, R¹¹And R¹²Ionic liquids are readily formed when they are of different structures. In this case, the difference in the number of carbon atoms is preferably 1 or more, more preferably 2 or more, and still more preferably 4 or more.

The organic cation containing a nitrogen atom is preferably an organic cation represented by the following formula (3), for example.

[ solution 4]

In the formula (3), R²¹～R²⁴Each independently an alkyl group having 1 to 20 carbon atoms or a group consisting of- (CH)₂)_kAlkoxyalkyl groups represented by-OR. k is 1 or 2. R is methyl or ethyl. Examples of the alkyl group and alkoxyalkyl group having 1 to 20 carbon atoms include the same groups as those described above.

In addition, R²¹～R²⁴Any two of which may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. Further, R²¹～R²⁴Any two of them may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and the remaining 2 may be bonded to each other to form a spiro ring in which the nitrogen atom is a spiro atom. In this case, examples of the ring include an aziridine ring, an azetidine ring, a pyrrolidine ring, a piperidine ring, and an azepane ring, and a pyrrolidine ring and a piperidine ring are preferred, and a pyrrolidine ring is more preferred. In addition, as the spiro ring, a1, 1' -spirobipyrrolidine ring is particularly preferable.

At R²¹～R²⁴When all of the alkyl groups are alkyl groups, at least one of the alkyl groups has a structure different from the other alkyl groups, and the ionic liquid is easily formed, and in this case, the difference in the number of carbon atoms is preferably 1 or more, more preferably 2 or more, and still more preferably 4 or more.

Specific examples of the nitrogen atom-containing organic cation represented by the formula (3) include a quaternary ammonium ion represented by the following formula (3-1) or (3-2), and a pyrrolidinium ion represented by the following formula (3-3) or (3-4).

[ solution 5]

In the formulae (3-1) to (3-4), R and k are the same as described above. R²⁰¹～R²⁰⁴Each independently is an alkyl group having 1 to 4 carbon atoms. R²⁰⁵And R²⁰⁶Each independently is an alkyl group having 1 to 4 carbon atoms. In addition, R²⁰⁵And R²⁰⁶May be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. Examples of the alkyl group having 1 to 4 carbon atoms include the same groups as those mentioned above.

As the organic cation containing a nitrogen atom, for example, an imidazolium ion represented by the following formula (4) is also preferable.

[ solution 6]

In the formula (4), R³¹And R³²Each independently an alkyl group having 1 to 20 carbon atoms or a group consisting of- (CH)₂)_kAlkoxyalkyl groups represented by-OR. R and k are the same as described above. Examples of the alkyl group and alkoxyalkyl group having 1 to 20 carbon atoms include the same groups as those described above. In this case, R³¹And R³²Ionic liquids are readily formed when different groups are present.

As the organic cation containing a nitrogen atom, for example, a pyridinium ion represented by the following formula (5) is also preferable.

[ solution 7]

In the formula (5), R⁴¹Is alkyl with 1-8 carbon atoms or is- (CH)₂)_kAlkoxyalkyl groups represented by-OR. R and k are the same as described above. Examples of the alkyl group and alkoxyalkyl group having 1 to 8 carbon atoms include the same groups as those described above.

The silyl ether-containing sulfonate of the present invention is an ionic liquid depending on the kind of cation. For example, the sulfonate salt whose cation is represented by the formula (3-4) is liable to become an ionic liquid, and in the cation represented by the formula (2), R is¹¹And R¹²The sulfonate being of different structure is readily availableBecoming an ionic liquid. In the present invention, the ionic liquid means a salt having a melting point of 100 ℃ or lower and consisting of only ions. The ionic liquid of the present invention comprising a silyl ether-containing sulfonate salt preferably has a melting point of room temperature (25 ℃) or lower (i.e., is liquid at room temperature). The ionic liquid of the present invention, which is composed of a silyl ether-containing sulfonate, has no halogen and therefore has a small environmental burden.

[ method for producing silyl ether-containing sulfonate ]

The silyl ether-containing sulfonate of the present invention can be produced, for example, according to the following scheme a.

[ solution 8]

(in the formula, R¹～R⁴M and n are the same as described above. M⁺Is a metal ion. A. the⁺Is a cation having a valence of 1. X^-Is a halogen ion. )

First, compound (1a) is reacted with a sulfonating agent to synthesize compound (1b) (step 1). Examples of the sulfonating agent include sodium bisulfite and the like. Furthermore, the compound (1a) can be synthesized with reference to J.org.chem.,1970,35, page 1308-1314. In addition, sulfonation can be carried out with reference to j.org.chem.,1961,26(6), page 2097-2098.

Examples of the solvent used in step 1 include pure water, or a mixed solvent obtained by adding an alcohol such as methanol or ethanol, or a hydrophilic solvent such as acetone or acetonitrile as an auxiliary solvent to water. The reaction temperature is usually about 10 to 50 ℃ and preferably about 20 to 30 ℃. The reaction time is usually about 1 to 7 days, preferably about 3 to 4 days.

Next, an ion exchange reaction between the compound (1b) and the compound (1c) is performed (step 2). Thereby, a salt containing an anion represented by formula (1) can be obtained.

The ion exchange reaction can be carried out by, for example, mixing an aqueous solution of the compound (1b) with an aqueous solution of the compound (1 c). The reaction temperature in this case is preferably 10 to 50 ℃ and more preferably around room temperature (about 25 ℃). The reaction time is usually about 3 to 4 days. When the compound (1b) and the compound (1c) are mixed, the mixture is not limited to an aqueous solution, and an organic solvent may be used as long as both are dissolved.

In the reaction of the 2 nd step, the use ratio of the compound represented by the formula (1b) to the compound represented by the formula (1c) is represented by a molar ratio, and can be set to 5: 1-1: about 5, and preferably, in terms of cost, the ratio of the total weight of the composition is close to 1: 1 in the ratio.

After the reaction is completed, the target product can be obtained by performing a usual post-treatment.

The silyl ether-containing sulfonate of the present invention can also be used as an electrolyte solution solvent, an electrolyte, and an additive for electrolytes in electric storage devices such as electric double layer capacitors, lithium ion capacitors, redox capacitors, lithium secondary batteries, lithium ion secondary batteries, lithium air batteries, and proton polymer batteries. In addition, the silyl ether-containing sulfonate of the present invention can also be used as a lubricant. The silyl ether-containing sulfonate of the present invention can also be used as an antistatic agent, a plasticizer, or the like to be added to a polymer material such as rubber or plastic. Further, the ionic liquid of the present invention, which is composed of a silyl ether-containing sulfonate, is a halogen-free ionic liquid and therefore can be used as a cleaning solvent with a small environmental burden.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. The analytical devices and conditions used in the examples are as follows.

[1]Nuclear magnetic resonance (¹H-NMR、¹³C-NMR、²⁹Si-NMR) spectrum

The device comprises the following steps: ECX-500 manufactured by Nippon electronics Co., Ltd. (¹H-NMR、¹³C-NMR、²⁹Si-NMR), or ECZ-400S (manufactured by Nippon electronics Co., Ltd.) (¹H-NMR)

Solvent: heavy hydrogenated dimethyl sulfoxide (DMSO-d)₆) Or deuterated chloroform (CDCl)₃)

[2] Melting Point

The device comprises the following steps: DSC6200 made by precision instruments

The measurement conditions were as follows: heating from 20 deg.C to 40 deg.C at 10 deg.C per minute, holding at 40 deg.C for 1 min, cooling from 40 deg.C to-100 deg.C at 1 deg.C per minute, holding at-100 deg.C for 1 min, and heating from-100 deg.C to 100 deg.C at 1 deg.C per minute.

[ examples 1 to 1]2- (1',1',3',3',3' -pentamethyldisiloxanyl) ethane-1-sulfonic acid sodium salt (MeSilC)₂SO₃Na) Synthesis

A three-necked flask equipped with a reflux condenser and a magnetic stirrer was degassed, and then charged with 7.3g (70.1mmol) of sodium hydrogen sulfite, 0.8g (11.5mmol) of sodium nitrite, 0.8g (9.4mmol) of sodium nitrate, 60mL of ion-exchanged water, 6.0g (34.7mmol) of pentamethylvinyldisiloxane and 130mL of methanol under a nitrogen stream, and vigorously stirred at room temperature for 3 days in a closed system. The precipitated solid was removed by suction filtration, methanol was distilled off from the filtrate by atmospheric distillation, and the precipitated colorless crystals were separated by filtration to obtain the objective compound MeSilC₂SO₃Na (yield 6.5g (17.7mmol), yield 51.0%).

¹H-NMR(DMSO-d₆,500MHz,δ)3.43(s,10H),2.37(m,2H),0.85(m,2H),0.05(s,9H),0.03(s,6H).

¹³C-NMR(DMSO-d₆,125Hz,δ)45.9(-CH₂-SO₃Na),13.8(-CH₂-CH₂-SO₃Na),2.2(-Si(CH₃)₃),0.3(-Si(CH₃)₂-).

²⁹Si-NMR(DMSO-d₆,100MHz,δ)8.0.

Examples 1 to 2]3- (1',1',3',3',3' -pentamethyldisiloxanyl) propane-1-sulfonic acid sodium salt (MeSilC)₃SO₃Na) Synthesis

MeSilC was obtained as a colorless solid in the same manner as in example 1-1, except that 5.1g (27.0mmol) of allylpentamethyldisiloxane was used in place of 6.0g of pentamethylvinyldisiloxane₃SO₃Na (yield 2.9g (9.8mmol), yield 36.4%).

¹H-NMR(DMSO-d₆,500MHz,δ)3.28(s,2H),2.32(m,2H),1.47(m,2H),0.38(m,2H),-0.08(s,9H),-0.11(s,6H).

¹³C-NMR(DMSO-d₆,125Hz,δ)55.1(-CH₂-SO₃Na),18.91(-CH₂-CH₂-SO₃Na),17.5(CH₂-CH₂-CH₂-SO₃Na),2.0(-Si(CH₃)₃),0.4(-Si(CH₃)₂-).

²⁹Si-NMR(DMSO-d₆,100MHz,δ)8.5.

Examples 1 to 3]2- (3' -n-butyl-1 ',1',3',3' -tetramethyldisiloxanyl) ethane-1-sulfonic acid sodium salt (BuSilC)₂SO₃Na) Synthesis

BuSilC was obtained as a colorless solid in the same manner as in example 1-1, except that 5.0g (21.8mmol) of 3-n-butyl-1, 1,3, 3-tetramethyl-1-vinyldisiloxane was used in place of 6.0g of pentamethylvinyldisiloxane₂SO₃Na (yield 5.2g (12.6mmol), yield 55.4%).

¹H-NMR(DMSO-d₆,500MHz,δ)3.65(s,10H),2.55(m,2H),1.45(m,4H),1.04(m,5H),0.66(m,2H),0.21(s,6H),0.20(s,6H).

¹³C-NMR(DMSO-d₆,125Hz,δ)45.9,25.8,25.1,17.6,13.7,0.5,0.3.

²⁹Si-NMR(DMSO-d₆,100MHz,δ)8.4,7.8.

Examples 1 to 4]3- (3' -n-butyl-1 ',1',3',3' -tetramethyldisiloxanyl) propane-1-sulfonic acid sodium salt (BuSilC)₃SO₃Na) Synthesis

BuSilC was obtained as a colorless solid in the same manner as in example 1-1, except that 5.0g (21.8mmol) of 1-allyl-3-n-butyl-1, 1,3, 3-tetramethyldisiloxane was used in place of 6.0g of pentamethylvinyldisiloxane₃SO₃Na (yield 5.0g (13.0mmol), yield 59.7%).

¹H-NMR(DMSO-d₆,500MHz,δ)3.46(s,6H),2.41(m,2H),1.87(m,2H),1.56(m,4H),0.13(t,3H),0.77(m,4H),0.30(s,12H).

¹³C-NMR(DMSO-d₆,125Hz,δ)55.0,25.8,25.2,19.0,17.7,13.8,0.5,0.4.

²⁹Si-NMR(DMSO-d₆,100MHz,δ)8.1,7.7.

Examples 1 to 5]2- [ bis (trimethylsiloxy) methylsilyl group]Ethane-1-sulfonic acid sodium salt (Me)₃SiO)₂SiC₂SO₃Na) Synthesis

Me (Me) was obtained as a colorless solid in the same manner as in example 1-1, except that 5.04g (20.3mmol) of bis (trimethylsiloxy) (methyl) (vinyl) silane was used₃SiO)₂SiC₂SO₃Na (yield 2.92g (8.28mmol), yield 40.8%).

¹H-NMR(DMSO-d₆,500MHz,δ)-0.01(s,3H),0.07(s,18H),0.77-0.81(m,2H),2.31-2.35(m,2H).

¹³C NMR(DMSO-d₆,125Hz,δ)-0.4,1.9,13.2,45.7.

[ example 2-1]Tributyldodecylphosphonium 2- (1',1',3',3',3' -pentamethyldisiloxanyl) ethane-1-sulfonate (BDDP MeSilC)₂SO₃) Synthesis of (2)

An eggplant-shaped schlenk flask equipped with a magnetic stirrer was degassed, and MeSilC was placed under an argon stream₂SO₃Na1.02g (3.05mmol) and 25mL of ion-exchanged water were stirred. 2.67g (3.28mmol) of a 50 mass% aqueous solution of tributyldodecylphosphonium chloride was added thereto, and the mixture was instantaneously clouded. After further stirring for 1 hour, the mixture was allowed to stand and was separated into 2-layered solutions. The aqueous layer was removed to make ethyl acetate an organic layer, which was extracted several times with ion-exchanged water and then dried over magnesium sulfate. Concentrating the extract by an evaporator, and distilling off the solvent under reduced pressure at 40-50 ℃ for 7 hours to obtain BDDP MeSilC as a colorless transparent viscous liquid₂SO₃(yield 1.68g (2.46mmol), yield 80.6%). Will be provided with¹The H-NMR spectrum is shown in FIG. 1, and the DSC spectrum is shown in FIG. 2.

¹H-NMR(CDCl₃,500MHz,δ)2.72(m,2H),2.29(m,8H),1.48(m,15H),1.21(m,16H),1.08(m,2H),0.93(t,9H),0.84(t,3H),0.01(s,6H),0.00(s,9H).

[ examples 2 to 2]2- (1',1',3',3',3' -Pentamethyldisiloxanyl) ethane-1-sulfonic acid tributylhexadecylphosphonium (BHDP MeSilC)₂SO₃) Synthesis of (2)

Except that MeSilC₂SO₃BHDP MeSilC as a colorless transparent viscous liquid was obtained in the same manner as in example 2-1 except that the amount of Na used was 1.04g (3.13mmol) and the amount of ion-exchanged water used was 20mL, and 2.99g (3.22mmol) of a 50 mass% aqueous solution of tributylhexadecylphosphonium chloride was used instead of the 50 mass% aqueous solution of tributyldodecylphosphonium chloride₂SO₃(yield 1.66g (2.43mmol), yield 77.6%). Will be provided with¹The H-NMR spectrum is shown in FIG. 3, and the DSC spectrum is shown in FIG. 4.

[ examples 2 to 3]3- (1',1',3',3',3' -pentamethyldisiloxanyl) propane-1-sulfonic acid tributyl dodecyl phosphonium (BDDP MeSilC)₃SO₃) Synthesis of (2)

Except for replacing MeSilC₂SO₃Na and MeSilC₃SO₃BDDP MeSilC as a colorless transparent viscous liquid was obtained in the same manner as in example 2-1 except that 0.52g (1.42mmol) of Na0, 5mL of ion-exchanged water and 1.31g (1.61mmol) of a 50 mass% aqueous solution of tributyldodecylphosphonium chloride were used₃SO₃(yield 0.43g (0.68mmol), yield 47.2%). Will be provided with¹The H-NMR spectrum is shown in FIG. 5, and the DSC is shown in FIG. 6.

¹H-NMR(CDCl₃,500MHz,δ)2.80(m,2H),2.32(m,8H),1.84(m,2H),1.50(m,16H),1.23(m,14H),0.95(t,9H),0.85(t,3H),0.56(m,2H),0.02(s,15H).

¹³C-NMR(CDCl₃,125MHz,δ)56.0,32.1,31.0(d,J＝15.5Hz),29.8,29.7,29.5,29.2,24.2(d,J＝15.5Hz),24.0(d,J＝4.8Hz),22.8,22.1(d,J＝4.8Hz),19.6,19.2(d,J＝46.5Hz),19.0(J＝46.5Hz),18.3,14.3,13.7,2.2,0.5.

[ examples 2 to 4]3- (1',1',3',3',3' -pentamethyldisiloxanyl) propane-1-sulfonic acid trisButylhexadecylphosphonium (BHDP MeSilC)₃SO₃) Synthesis of (2)

Except for replacing MeSilC₂SO₃Na and MeSilC₃SO₃BHDP MeSilC as a colorless transparent viscous liquid was obtained in the same manner as in example 2-2 except that 0.52g (1.42mmol) of Na0, 5mL of ion-exchanged water and 1.45g (1.56mmol) of a 50 mass% aqueous solution of tributylhexadecylphosphonium chloride were used₃SO₃(yield 0.15g (0.22mmol), yield 15.3%). Will be provided with¹The H-NMR spectrum is shown in FIG. 7, and the DSC spectrum is shown in FIG. 8.

[ examples 2 to 5]2- (3' -n-butyl-1 ',1',3',3' -tetramethyldisiloxanyl) ethane-1-sulfonic acid tributyl dodecyl phosphonium (BDDP BuSilC)₂SO₃) Synthesis of (2)

Except for replacing MeSilC₂SO₃Using BuSilC as Na₂SO₃BDDP BuSilC was obtained as a colorless transparent viscous liquid in the same manner as in example 2-1 except that 0.51g (1.44mmol) of Na0, 10mL of ion exchange water and 1.23g (1.51mmol) of a 50 mass% aqueous solution of tributyldodecylphosphonium chloride were used₂SO₃(yield 0.33g (0.48mmol), yield 33.3%). Will be provided with¹The H-NMR spectrum is shown in FIG. 9, and the DSC spectrum is shown in FIG. 10.

[ examples 2 to 6]2- (3' -n-butyl-1 ',1',3',3' -tetramethyldisiloxanyl) ethane-1-sulfonic acid tributylhexadecylphosphonium (BHDP BuSilC)₂SO₃) Synthesis of (2)

Except for replacing MeSilC₂SO₃Using BuSilC as Na₂SO₃BHDP BuSilC as a colorless transparent viscous liquid was obtained in the same manner as in example 2-2 except that 0.60g (1.62mmol) of Na0.60g, 10mL of ion exchange water and 1.59g (1.72mmol) of a 50 mass% aqueous solution of tributylhexadecylphosphonium chloride were used₂SO₃(yield 0.64g (0.88mmol), yield 54.3%). Will be provided with¹The H-NMR spectrum is shown in FIG. 11, and the DSC is shown in FIG. 12.

Examples 2 to 7]3- (3' -n-butyl-1 ',1',3',3' -tetramethylbenzidineTributyldodecylphosphonium disiloxane-based propane-1-sulfonate (BDDP BuSilC)₃SO₃) Synthesis of (2)

Except for replacing MeSilC₂SO₃Using BuSilC as Na₃SO₃BDDP BuSilC as a colorless transparent viscous liquid was obtained in the same manner as in example 2-1 except that 1.03g (2.52mmol) of Na1.52 was used, 10mL of ion exchange water was used, and 2.22g (2.73mmol) of a 50 mass% aqueous solution of tributyldodecylphosphonium chloride was used₃SO₃(yield 0.71g (1.06mmol), yield 42.0%). Will be provided with¹The H-NMR spectrum is shown in FIG. 13, and the DSC is shown in FIG. 14.

Examples 2 to 8]3- (3' -n-butyl-1 ',1',3',3' -tetramethyldisiloxanyl) propane-1-sulfonic acid tributylhexadecylphosphonium (BHDP BuSilC)₃SO₃) Synthesis of (2)

Except for replacing MeSilC₂SO₃Using BuSilC as Na₃SO₃BHDP BuSilC as a colorless transparent viscous liquid was obtained in the same manner as in example 2-2 except that the amount of Na0.51g (1.46mmol) used was changed to 10mL for the amount of ion-exchanged water and 1.36g (1.47mmol) for the amount of a 50 mass% aqueous solution of tributylhexadecylphosphonium chloride₃SO₃(yield 0.75g (1.01mmol), yield 69.1%). Will be provided with¹The H-NMR spectrum is shown in FIG. 15, and the DSC is shown in FIG. 16.

Examples 2 to 9]2- [ bis (trimethylsiloxy) methylsilyl group]Ethane-1-sulfonic acid tributyl dodecyl phosphonium (BDDP Me (Me))₃SiO)₂SiC₂SO₃) Synthesis of (2)

Except for replacing MeSilC₂SO₃Na and Me (Me)₃SiO)SiC₂SO₃BDDP Me (Me) was obtained as a colorless transparent viscous liquid in the same manner as in example 2-1 except that 0.53g (1.25mmol) of Na0, 10mL of ion-exchanged water was used, and 1.06g (1.30mmol) of a 50 mass% aqueous solution of tributyldodecylphosphonium chloride was used₃SiO)₂SiC₂SO₃(yield 0.40g (0.57mmol), yield 45.5%). Will be provided with¹The H-NMR spectrum is shown inIn fig. 17, DSC is illustrated in fig. 18.

Examples 2 to 10]2- [ bis (trimethylsiloxy) methylsilyl group]Ethane-1-sulfonic acid tributyl hexadecyl phosphonium (BHDP Me (Me))₃SiO)₂SiC₂SO₃) Synthesis of (2)

Except for replacing MeSilC₂SO₃Na and Me (Me)₃SiO)₂SiC₂SO₃BHDP Me (Me) as a colorless transparent viscous liquid was obtained in the same manner as in example 2-2 except that the amount of Na1.00g (2.34mmol) used was changed to 18mL of ion-exchanged water and the amount of a 50 mass% aqueous solution of tributylhexadecylphosphonium chloride was changed to 2.20g (2.37mmol)₃SiO)₂SiC₂SO₃(yield 0.48g (0.63mmol), yield 27.0%). Will be provided with¹The H-NMR spectrum is shown in FIG. 19, and the DSC chart is shown in FIG. 20.

Examples 2 to 11]2- (1',1',3',3',3' -pentamethyldisiloxanyl) ethane-1-sulfonic acid N-2-methoxyethyl-N-methylpyrrolidinium (MEMP MeSilC)₂SO₃) Synthesis of (2)

MeSilC was placed in a eggplant-shaped flask equipped with a magnetic stirrer₂SO₃Na1.17g (4.20mmol) and acetonitrile 10mL, stirring. To this was added 0.67g (3.82mmol) of N-2-methoxyethyl-N-methylpyrrolidinium chloride dissolved in 2mL of acetonitrile. After stirring overnight, the precipitated fractions were separated by filtration. The filtrate was concentrated using an evaporator and then a vacuum pump to obtain a colorless transparent viscous liquid, which was designated as MEMP MeSilC₂SO₃(yield 1.52g (3.80mmol), yield 99.5%). Will be provided with¹The H-NMR spectrum is shown in FIG. 21, and the DSC spectrum is shown in FIG. 22.

The melting point and the shape at 25 ℃ of each silyl ether containing sulfonate determined by DSC measurement are shown in Table 1.

[ Table 1]

Examples		Melting Point (. degree.C.)	Shape of
				2-1	BDDP MeSilC2SO3	9℃	Colorless transparent viscous liquid
2-2	BHDP MeSilC2SO3	21℃	Colorless transparent viscous liquid
				2-3	BDDP MeSilC3SO3	2℃	Colorless transparent viscous liquid
2-4	BHDP MeSilC3SO3	-5℃	Colorless transparent viscous liquid
				2-5	BDDP BuSilC2SO3	-1℃	Colorless transparent viscous liquid
2-6	BHDP BuSilC2SO3	-2℃	Colorless transparent viscous liquid
				2-7	BDDP BuSilC3SO3	-4℃	Colorless transparent viscous liquid
2-8	BHDP BuSilC3SO3	-3℃	Colorless transparent viscous liquid
				2-9	BDDP Me(Me3SiO)2SiC2SO3	-13℃	Colorless transparent viscous liquid
2-10	BHDP Me(Me3SiO)2SiC2SO3	3℃	Colorless transparent viscous liquid
				2-11	MEMP MeSilC2SO3	8℃	Colorless transparent viscous liquid