JP2010285398A - Super heat-resistant ionic liquid - Google Patents
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- JP2010285398A JP2010285398A JP2009141547A JP2009141547A JP2010285398A JP 2010285398 A JP2010285398 A JP 2010285398A JP 2009141547 A JP2009141547 A JP 2009141547A JP 2009141547 A JP2009141547 A JP 2009141547A JP 2010285398 A JP2010285398 A JP 2010285398A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 230000004580 weight loss Effects 0.000 claims description 7
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 6
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- -1 tetrafluboroborate Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229960003080 taurine Drugs 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003957 anion exchange resin Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 3
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 3
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- SNKZJIOFVMKAOJ-UHFFFAOYSA-N 3-Aminopropanesulfonate Chemical compound NCCCS(O)(=O)=O SNKZJIOFVMKAOJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QNALZNMQKPAXNA-UHFFFAOYSA-M dodecyl(trimethyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[P+](C)(C)C QNALZNMQKPAXNA-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- QCLVFLIIJODTJU-UHFFFAOYSA-N triethyl(octyl)phosphanium Chemical compound CCCCCCCC[P+](CC)(CC)CC QCLVFLIIJODTJU-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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Abstract
Description
本発明は、超耐熱性イオン液体に関する。 The present invention relates to a super heat-resistant ionic liquid.
イオン液体とは融点が１００℃程度以下の溶融塩の総称であるが、近年、その極めて低い蒸気圧のため潤滑油として、また高温反応において繰り返し使用可能な反応溶媒として注目されている（例えば、非特許文献１参照）。 An ionic liquid is a general term for a molten salt having a melting point of about 100 ° C. or less, but has recently attracted attention as a lubricating oil because of its extremely low vapor pressure and as a reaction solvent that can be used repeatedly in high-temperature reactions (for example, Non-patent document 1).
イオン液体はカチオンとアニオンとから構成されるが、代表的なカチオンとしては、ジアルキルイミダゾリウム、アルキルピリジニウム、テトラアルキルアンモニウム、環状のピロリジニウムなどが知られている。一方アニオンとしては、塩化物、臭化物、ヨウ化物などのハロゲン化物やテトラフルホロボレート、テトラフルオロホスフェート、トリフルオロメタンスルホネートやビス（トリフルオロメタンスルホニル）イミドなどの含フッ素系アニオンが多く報告されている（例えば、非特許文献２参照）。 The ionic liquid is composed of a cation and an anion. As typical cations, dialkylimidazolium, alkylpyridinium, tetraalkylammonium, cyclic pyrrolidinium, and the like are known. On the other hand, as anions, many halides such as chloride, bromide and iodide, and fluorine-containing anions such as tetrafluboroborate, tetrafluorophosphate, trifluoromethanesulfonate and bis (trifluoromethanesulfonyl) imide have been reported ( For example, refer nonpatent literature 2).
ところで、例えば潤滑油として用いられるイオン液体は、高温での使用に耐えられるように、耐熱性に優れることが望ましいが、耐熱性に優れたイオン液体は通常分子内にハロゲン元素を含んでいる。ハロゲン元素を含むイオン液体を高温で使用した場合には、フッ酸や塩酸などが発生し、配管腐食などを引き起こすおそれがあるため、実際に潤滑油として使用することは困難である。
また、例えば反応溶媒として用いられる一般的な有機溶媒（アセトンやアセトニトリル）は、蒸気圧が高いために高温での反応において気化してしまう。気化を防ぐために高圧とすると高温・高圧条件に耐えられず溶媒が分解してしまうため、繰り返し使用することが困難であり、使い捨てにせざるを得ない。
By the way, for example, an ionic liquid used as a lubricating oil desirably has excellent heat resistance so that it can be used at high temperatures, but an ionic liquid having excellent heat resistance usually contains a halogen element in the molecule. When an ionic liquid containing a halogen element is used at a high temperature, hydrofluoric acid, hydrochloric acid, etc. are generated, which may cause pipe corrosion and the like, so it is difficult to actually use it as a lubricating oil.
Further, for example, a general organic solvent (acetone or acetonitrile) used as a reaction solvent is vaporized in a reaction at a high temperature because of a high vapor pressure. If a high pressure is used to prevent vaporization, the solvent will decompose without being able to withstand the high temperature and high pressure conditions, so that it is difficult to use repeatedly, and it must be disposable.
さらに、ビス（トリフルオロメタンスルホニル）イミドを含むイオン液体は耐熱性に優れていることが知られているが、このようなイオン液体は疎水性であり、親水性で耐熱性に優れた（例えば、５％重量減少温度が３９０℃以上である）イオン液体は知られていなかった。 Furthermore, ionic liquids containing bis (trifluoromethanesulfonyl) imide are known to have excellent heat resistance, but such ionic liquids are hydrophobic, hydrophilic and excellent in heat resistance (for example, No ionic liquid has been known (5% weight loss temperature is 390 ° C. or higher).
そこで本発明は、親水性であり、かつ耐熱性に優れる非ハロゲン系のイオン液体を提供することを目的とする。 Accordingly, an object of the present invention is to provide a non-halogen ionic liquid that is hydrophilic and has excellent heat resistance.
本発明は、下記一般式（Ｉ）で表されるホスホニウム塩からなるイオン液体を提供する。 The present invention provides an ionic liquid comprising a phosphonium salt represented by the following general formula (I).
［式（Ｉ）中、Ｒ１〜Ｒ４はそれぞれ独立に炭素数１〜１２の環状、直鎖又は分岐状のアルキル基を示し、Ｘは炭素数１〜１０のアルキレン基を示す。］
[In formula (I), R < 1 > -R < 4 > shows a C1-C12 cyclic, linear or branched alkyl group each independently, and X shows a C1-C10 alkylene group. ]
かかるイオン液体は、非ハロゲン系であるにもかかわらず、親水性であり、かつ耐熱性に優れる。 Such an ionic liquid is hydrophilic and excellent in heat resistance despite being non-halogen.
上記Ｘはエチレン基であると好ましく、上記Ｒ１〜Ｒ４は炭素数１〜６の直鎖又は分岐状のアルキル基であると好ましい。 X is preferably an ethylene group, and R 1 to R 4 are preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
上記イオン液体においては、５％重量減少温度が３９０℃以上であることが好ましい。なお、「５％重量減少温度」は、例えば実施例に記載の方法により測定されるものをいう。 In the ionic liquid, the 5% weight loss temperature is preferably 390 ° C. or higher. The “5% weight loss temperature” refers to that measured by the method described in the examples, for example.
本発明によれば、非ハロゲン系であるにもかかわらず、親水性であり、かつ耐熱性に優れるイオン液体を提供することができる。
かかるイオン液体は、気体のキャリアとして使用することができる。また、本発明のイオン液体は、親水性であるので、水系切削油や水系作動油などの水系潤滑油として好適に使用することができる。
さらに、本発明のイオン液体は、耐熱性に優れるので、繰り返し使用可能な反応溶媒として使用することができる。アセトンやアセトニトリル等の使い捨てで使用する溶媒に代えて、本発明のイオン液体を反応溶媒として用いると、反応溶媒の使用量を大幅に削減することができ、環境保護の観点から非常に好ましい。
According to the present invention, it is possible to provide an ionic liquid that is hydrophilic and excellent in heat resistance despite being non-halogen.
Such ionic liquids can be used as gaseous carriers. Moreover, since the ionic liquid of the present invention is hydrophilic, it can be suitably used as an aqueous lubricant such as an aqueous cutting oil or an aqueous hydraulic oil.
Furthermore, since the ionic liquid of the present invention is excellent in heat resistance, it can be used as a reaction solvent that can be used repeatedly. When the ionic liquid of the present invention is used as a reaction solvent instead of a disposable solvent such as acetone or acetonitrile, the amount of the reaction solvent used can be greatly reduced, which is very preferable from the viewpoint of environmental protection.
以下、本発明の一実施形態について詳述するが、本発明は以下の実施形態に限定されるものではない。 Hereinafter, one embodiment of the present invention will be described in detail, but the present invention is not limited to the following embodiment.
上記式（Ｉ）において、Ｒ１〜Ｒ４は、炭素数１〜１２の環状、直鎖又は分岐状のアルキル基であり、炭素数１〜６の直鎖又は分岐状のアルキル基であると好ましい。直鎖又は分岐状のアルキル基の炭素数は、１〜４個であると好ましく、１，２，４個であるとより好ましい。 In the above formula (I), R 1 ~R 4, the annular having 1 to 12 carbon atoms, a linear or branched alkyl group, when a linear or branched alkyl group having 1 to 6 carbon atoms preferable. The linear or branched alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1, 2, 4 carbon atoms.
炭素数１〜１２の環状、直鎖又は分岐状のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、ドデシル基、シクロヘキシル基が挙げられ、好ましくはメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基であり、より好ましくはメチル基、エチル基、ｎ−ブチル基である。 Examples of the cyclic, linear or branched alkyl group having 1 to 12 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, and pentyl group. Hexyl group, octyl group, dodecyl group and cyclohexyl group, preferably methyl group, ethyl group, propyl group, isopropyl group and n-butyl group, more preferably methyl group, ethyl group and n-butyl group. It is.
上記式（Ｉ）において、Ｘは、炭素数１〜１０のアルキレン基であり、炭素数１〜６のアルキレン基であると好ましく、炭素数２〜４のアルキレン基であるとより好ましい。 In the above formula (I), X is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
炭素数１〜１０のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基が挙げられ、エチレン基、プロピレン基、ブチレン基であると好ましく、エチレン基であるとより好ましい。 Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, preferably an ethylene group, a propylene group, and a butylene group. More preferably.
（ホスホニウム塩の一般的製造方法）
上記ホスホニウム塩は、例えば以下に示す方法で製造することができる。
陰イオン交換樹脂（ＯＨ体）に対して、上記式（Ｉ）のアニオン部に対応するアミノスルホン酸を水溶液として展開して、陰イオン交換樹脂のＯＨ−部分をアミノスルホン酸由来のアニオンで置換する。続いて、上記式（Ｉ）のカチオン部に対応するテトラアルキルホスホニウムハライド、好ましくはテトラアルキルホスホニウムブロミドの水溶液を陰イオン交換樹脂に通し、得られた混合溶液における溶媒を減圧留去し、残渣から適当な方法で未反応のアミノスルホン酸を除去することで、所望のイオン液体が得られる。
(General production method of phosphonium salt)
The phosphonium salt can be produced, for example, by the method shown below.
For the anion exchange resin (OH form), the aminosulfonic acid corresponding to the anion moiety of the above formula (I) is developed as an aqueous solution, and the OH - part of the anion exchange resin is replaced with an anion derived from aminosulfonic acid. To do. Subsequently, an aqueous solution of a tetraalkylphosphonium halide corresponding to the cation moiety of the above formula (I), preferably an aqueous solution of tetraalkylphosphonium bromide, is passed through an anion exchange resin, and the solvent in the obtained mixed solution is distilled off under reduced pressure. The desired ionic liquid is obtained by removing unreacted aminosulfonic acid by an appropriate method.
上記アミノスルホン酸としては、例えばアミノメタンスルホン酸、２−アミノエタンスルホン酸（タウリン）、３−アミノプロパンスルホン酸を用いることができ、２−アミノエタンスルホン酸を用いると好ましい。 As the aminosulfonic acid, for example, aminomethanesulfonic acid, 2-aminoethanesulfonic acid (taurine), 3-aminopropanesulfonic acid can be used, and 2-aminoethanesulfonic acid is preferably used.
上記カチオン部に対応するテトラアルキルホスホニウムハライドとしては、例えばテトラメチルホスホニウムブロミド、テトラエチルホスホニウムブロミド、テトラブチルホスホニウムブロミド、オクチルトリエチルホスホニウムブロミド、ドデシルトリメチルホスホニウムブロミド、トリオクチルエチルホスホニウムブロミド；これらのブロミドに対応するクロリドを用いることができ、テトラメチルホスホニウムブロミド、テトラエチルホスホニウムブロミド、テトラブチルホスホニウムブロミドを用いると好ましい。 Examples of the tetraalkylphosphonium halide corresponding to the cation moiety include tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, octyltriethylphosphonium bromide, dodecyltrimethylphosphonium bromide, trioctylethylphosphonium bromide; Chloride can be used, and tetramethylphosphonium bromide, tetraethylphosphonium bromide, and tetrabutylphosphonium bromide are preferably used.
また、上記式（Ｉ）のカチオン部に対応するテトラアルキルホスホニウムヒドロキシドが、例えばテトラブチルホスホニウムヒドロキシドのように、水酸化物又はその水溶液の形で市販されている場合には、上記ホスホニウム塩を以下の製造方法により製造することもできる。
テトラアルキルホスホニウムヒドロキシドの水溶液に対して、上記式（Ｉ）のアニオン部に対応するアミノスルホン酸を滴下し、室温で攪拌する。得られた混合溶液の溶媒を減圧留去し、残渣から適当な方法で未反応のアミノスルホン酸を除去することで、所望のイオン液体が得られる。
When the tetraalkylphosphonium hydroxide corresponding to the cation moiety of the above formula (I) is commercially available in the form of a hydroxide or an aqueous solution thereof such as tetrabutylphosphonium hydroxide, the phosphonium salt Can also be produced by the following production method.
Aminosulfonic acid corresponding to the anion moiety of the above formula (I) is dropped into an aqueous solution of tetraalkylphosphonium hydroxide and stirred at room temperature. The solvent of the obtained mixed solution is distilled off under reduced pressure, and the unreacted aminosulfonic acid is removed from the residue by an appropriate method, whereby a desired ionic liquid is obtained.
上述のイオン液体は、特に耐熱性に優れ、その５％重量減少温度は好ましくは３９０℃以上である。 The above-mentioned ionic liquid is particularly excellent in heat resistance, and its 5% weight loss temperature is preferably 390 ° C. or higher.
以下、実施例によって本発明をより具体的に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to this.
（実施例１）
タウリン１．３ｇに水１３ｍＬを加え、均一溶解させた後にこれを陰イオン交換樹脂（ＯＨ体）に通した。テトラメチルホスホニウムブロミド１．２ｇをイオン交換水２０ｍＬに均一溶解させ、先ほどの陰イオン交換樹脂に通した。得られた水溶液を減圧乾燥し、これにアセトニトリル２０ｍｌとメタノール５ｍｌを加えて氷冷し、沈殿した未反応のタウリンをろ別した。得られたろ液を減圧乾燥することにより、テトラメチルホスホニウムタウリン塩１．５ｇ（収率９９％）を得た。本品の１Ｈ−ＮＭＲ測定を行った結果は図１に示したとおりであり、プロトンの化学シフトと積分強度から目的物の生成が確認された。
Example 1
After adding 13 mL of water to 1.3 g of taurine and dissolving it uniformly, this was passed through an anion exchange resin (OH form). Tetramethylphosphonium bromide 1.2 g was uniformly dissolved in 20 mL of ion exchange water and passed through the anion exchange resin. The obtained aqueous solution was dried under reduced pressure, 20 ml of acetonitrile and 5 ml of methanol were added thereto, and the mixture was cooled with ice, and the precipitated unreacted taurine was separated by filtration. The obtained filtrate was dried under reduced pressure to obtain 1.5 g (99% yield) of tetramethylphosphonium taurine salt. The result of 1 H-NMR measurement of this product is as shown in FIG. 1, and the production of the target product was confirmed from the chemical shift of the proton and the integrated intensity.
（実施例２）
タウリン２ｇに水１３ｍＬを加え、均一溶解させた後にこれを陰イオン交換樹脂（ＯＨ体）に通した。テトラエチルホスホニウムブロミド２．３ｇをイオン交換水２０ｍＬに均一溶解させ、先ほどの陰イオン交換樹脂に通した。得られた水溶液を減圧乾燥し、これにアセトニトリル２０ｍｌとメタノール５ｍｌを加えて氷冷し、沈殿した未反応のタウリンをろ別した。得られたろ液を減圧乾燥することにより、テトラエチルホスホニウムタウリン塩２．６ｇ（収率９６％）を得た。本品の１Ｈ−ＮＭＲ測定を行った結果は図２に示したとおりであり、プロトンの化学シフトと積分強度から目的物の生成が確認された。
(Example 2)
After adding 13 mL of water to 2 g of taurine and uniformly dissolving it, it was passed through an anion exchange resin (OH form). 2.3 g of tetraethylphosphonium bromide was uniformly dissolved in 20 mL of ion exchange water and passed through the anion exchange resin. The obtained aqueous solution was dried under reduced pressure, 20 ml of acetonitrile and 5 ml of methanol were added thereto, and the mixture was cooled with ice, and the precipitated unreacted taurine was separated by filtration. The obtained filtrate was dried under reduced pressure to obtain 2.6 g (yield 96%) of tetraethylphosphonium taurine salt. The result of 1 H-NMR measurement of this product is as shown in FIG. 2, and the production of the target product was confirmed from the chemical shift of the proton and the integrated intensity.
（実施例３）
テトラブチルホスホニウムヒドロキシドの４０％水溶液６．９ｇに対してタウリン１．５ｇを加え、室温で１時間攪拌した。得られた混合溶液の溶媒を減圧留去し、これにアセトニトリル２０ｍｌとメタノール５ｍｌを加えて氷冷し、沈殿した未反応のタウリンをろ別した。得られたろ液を減圧乾燥することにより、テトラブチルホスホニウムタウリン塩３．８ｇ（収率９９％）を得た。本品の１Ｈ−ＮＭＲ測定を行った結果は図３に示したとおりであり、プロトンの化学シフトと積分強度から目的物の生成が確認された。
(Example 3)
To 6.9 g of 40% aqueous solution of tetrabutylphosphonium hydroxide, 1.5 g of taurine was added and stirred at room temperature for 1 hour. The solvent of the obtained mixed solution was distilled off under reduced pressure, 20 ml of acetonitrile and 5 ml of methanol were added thereto, and the mixture was ice-cooled, and precipitated unreacted taurine was separated by filtration. The obtained filtrate was dried under reduced pressure to obtain 3.8 g of tetrabutylphosphonium taurine salt (yield 99%). The result of 1 H-NMR measurement of this product is as shown in FIG. 3, and the production of the target product was confirmed from the chemical shift of the proton and the integrated intensity.
［５％熱重量減少温度の測定］
実施例で得られた化合物について、５％熱重量減少温度を測定した。なお、５％熱重量減少温度とは、試料を１２０℃で６時間乾燥させた後、熱重量測定装置（島津製作所製、商品名：ＴＧＡ−５０）で５０℃から５℃／分で昇温したときに、初期質量の５質量％だけ質量が減少したときの温度である。
[Measurement of 5% thermal weight loss temperature]
About the compound obtained in the Example, the thermal weight loss temperature of 5% was measured. The 5% thermogravimetric temperature decrease means that the sample was dried at 120 ° C. for 6 hours and then heated from 50 ° C. to 5 ° C./min with a thermogravimetric measuring device (trade name: TGA-50 manufactured by Shimadzu Corporation). Is the temperature when the mass is reduced by 5% by mass of the initial mass.
実施例１のテトラメチルホスホニウムタウリン塩の５％熱重量減少温度は３９４．１℃であり、実施例２のテトラエチルホスホニウムタウリン塩の５％熱重量減少温度は３９３．７℃であり、実施例３のテトラブチルホスホニウムタウリン塩の５％熱重量減少温度は３９２．５℃であり、いずれも耐熱性に優れることが明らかとなった。
The 5% thermogravimetric decrease temperature of the tetramethylphosphonium taurine salt of Example 1 is 394.1 ° C., and the 5% thermogravimetric decrease temperature of the tetraethylphosphonium taurine salt of Example 2 is 393.7 ° C. The tetrabutylphosphonium taurine salt had a 5% thermogravimetric decrease temperature of 392.5 ° C., and it was revealed that both had excellent heat resistance.
Claims (4)
［式（Ｉ）中、Ｒ１〜Ｒ４はそれぞれ独立に炭素数１〜１２の環状、直鎖又は分岐状のアルキル基を示し、Ｘは炭素数１〜１０のアルキレン基を示す。］ An ionic liquid comprising a phosphonium salt represented by the following general formula (I).
[In formula (I), R < 1 > -R < 4 > shows a C1-C12 cyclic, linear or branched alkyl group each independently, and X shows a C1-C10 alkylene group. ]
The ionic liquid according to any one of claims 1 to 3, wherein the 5% weight loss temperature is 390 ° C or higher.
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