JP4766914B2 - Cyclic ionic liquid containing S and method for producing the same - Google Patents
Cyclic ionic liquid containing S and method for producing the same Download PDFInfo
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- JP4766914B2 JP4766914B2 JP2005137441A JP2005137441A JP4766914B2 JP 4766914 B2 JP4766914 B2 JP 4766914B2 JP 2005137441 A JP2005137441 A JP 2005137441A JP 2005137441 A JP2005137441 A JP 2005137441A JP 4766914 B2 JP4766914 B2 JP 4766914B2
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- 239000002608 ionic liquid Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000004122 cyclic group Chemical group 0.000 title description 7
- 239000007788 liquid Substances 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 10
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 description 18
- 125000001424 substituent group Chemical group 0.000 description 18
- 125000000623 heterocyclic group Chemical group 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 11
- 125000005843 halogen group Chemical group 0.000 description 11
- 125000000753 cycloalkyl group Chemical group 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- -1 ammonium cations Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 5
- 125000000304 alkynyl group Chemical group 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- 0 **C1N(*)C(*)(*)C(*)(*)*1 Chemical compound **C1N(*)C(*)(*)C(*)(*)*1 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QFGRBBWYHIYNIB-UHFFFAOYSA-N 2-methylsulfanyl-4,5-dihydro-1,3-thiazole Chemical compound CSC1=NCCS1 QFGRBBWYHIYNIB-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Hybrid Cells (AREA)
- Fuel Cell (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Description
本発明は、低温からの広範な温度領域において液状を呈するイオン液体およびその製造方法と、それを利用した蓄電用デバイス、リチウム二次電池、電気二重層キャパシター、色素増感型太陽電池、燃料電池または反応溶媒に関する。 The present invention relates to an ionic liquid that exhibits a liquid state in a wide temperature range from a low temperature, a method for producing the same, a power storage device using the ionic liquid, a lithium secondary battery, an electric double layer capacitor, a dye-sensitized solar cell, and a fuel cell. Or relates to a reaction solvent.
アンモニウム系カチオンに代表されるようなＮ原子を含むオニウムをカチオンとして形成されるイオン液体は、従来から多数報告されているが、２０℃を超える温度においては液状を呈するものの、２０℃以下で液体として存在するものはごく一部である。そのため、室温付近においては、単独では電解質としても溶媒としても使用しにくいという状況である。（特許文献１、特許文献２および非特許文献１〜３参照）
すなわち、低温域において安定した液状を示すイオン液体が少ないことが、リチウム二次電池、電気二重層キャパシター、燃料電池あるいは色素増感型太陽電池、または蓄電用デバイス向け電解質あるいは添加剤としての応用に関し大きな障害となっている。
A large number of ionic liquids formed using onium-containing onium cations as typified by ammonium cations have been reported in the past, but they are liquid at temperatures above 20 ° C, but are liquid at temperatures below 20 ° C. Only a few are present. Therefore, in the vicinity of room temperature, it is difficult to use alone as an electrolyte or a solvent. (See Patent Document 1, Patent Document 2, and Non-Patent Documents 1 to 3)
That is, the fact that there are few ionic liquids that exhibit a stable liquid state in a low temperature range relates to applications as electrolytes or additives for lithium secondary batteries, electric double layer capacitors, fuel cells or dye-sensitized solar cells, or storage devices. It has become a major obstacle.
本発明は、低温からの広範な温度領域において安定な液状を呈すると共に、良好な導電率を有するイオン液体とその製造方法を提供することを目的とし、更には、上記のようなリチウム二次電池、電気二重層キャパシター、色素増感型太陽電池、燃料電池または反応溶媒等に使用する材料としての利用が可能なイオン液体を提供することを目的とするものであって、具体的には、Ｓ原子またはＯ原子を有する環状カチオンからなるイオン液体を提供することを目的とする。 An object of the present invention is to provide an ionic liquid that exhibits a stable liquid state in a wide temperature range from a low temperature and has a good electrical conductivity, and a method for producing the ionic liquid. Further, the lithium secondary battery as described above is provided. The object of the present invention is to provide an ionic liquid that can be used as a material used for an electric double layer capacitor, a dye-sensitized solar cell, a fuel cell, a reaction solvent, or the like. An object is to provide an ionic liquid comprising a cyclic cation having atoms or O atoms.
本発明者らは、カチオン成分とアニオン成分からなる多数の塩を合成し、上記目的を達成するためのイオン液体について鋭意検討した結果、下記一般式（１）で示される有機物カチオンを含む塩が、低温からの広範な温度領域で液体状態を呈すると共に、優れた導電性を有するイオン液体を構成することを見出した。 As a result of synthesizing a large number of salts composed of a cation component and an anion component and intensively studying an ionic liquid for achieving the above object, the present inventors have found a salt containing an organic cation represented by the following general formula (1). The present inventors have found that an ionic liquid which exhibits a liquid state in a wide temperature range from a low temperature and has excellent conductivity is formed.
[式中の置換基Ｒ1 〜Ｒ6 は、互いに独立しており、同一であっても異なっていても良い。置換基Ｒ1 〜Ｒ6 はそれぞれ、Ｈ原子、C1〜C30 の直鎖状または側鎖を有するアルキル基、C2〜C30 の単一もしくは複数の二重結合を持つ直鎖状または側鎖を有するアルケニル基、C2〜C30 の単一もしくは複数の三重結合を持つ直鎖状または側鎖を有するアルキニル基、飽和状態または部分的にもしくは完全に不飽和状態のシクロアルキル基、アリール基、アルコキシアルキル基、複素環基のいずれかを示す。また、これらの置換基Ｒ1 〜Ｒ6 のうちの単一または複数の置換基に含まれるＨ原子は、ハロゲン原子によって部分的にもしくは完全に置換でき、あるいは、ＣＮ基、ＮＯ2 基によって部分的に置換できる。また、Ｒ3 〜Ｒ6 は、Ｃ1 および／またはＣ2 原子と共同して環状構造または芳香環構造または複素環構造を形成してもよい。更に、Ｒ2 およびＲ3 は、Ｃ1 および／またはＮ原子と共同して環状構造または芳香環構造または複素環構造を形成することもできる。これらの置換基Ｒ1 〜Ｒ6 に含まれる炭素原子は、-O-, -C(O)-,-C(O)O-,-S-,-S(O)-,-SO2-,-SO3-,-N=,-N=N-,-NH-,-NR'-,-N(R')2, -PR'-,-P(O)R'-,-P(O)R'-O-,-O-P(O)R'-O-,および-P(R')2=N-の群から選択される原子および／または原子団によって置換できる（ここで、R'はC1〜C10 の直鎖状または側鎖を有するアルキル基、またはＦ原子によって部分的もしくは完全に置換されたアルキル基、飽和状態または部分的にもしくは完全に不飽和状態のシクロアルキル基、非置換もしくは置換されたフェニル基、または非置換もしくは置換されたヘテロシクルスを示す）。ＸおよびＹは、それぞれ独立して、Ｓ原子またはＯ原子を示す。更に、点線は、共役構造を示す。] [Substituents R 1 to R 6 in the formula are independent of each other and may be the same or different. Substituents R 1 to R 6 are each an H atom, a C 1 to C 30 straight chain or an alkyl group having a side chain, a C 2 to C 30 single chain or a straight chain having a plurality of double bonds, or An alkenyl group having a side chain, a linear or side chain alkynyl group having a C 2 to C 30 single or multiple triple bond, a saturated or partially or fully unsaturated cycloalkyl group, An aryl group, an alkoxyalkyl group, or a heterocyclic group is shown. In addition, the H atom contained in one or a plurality of substituents among these substituents R 1 to R 6 can be partially or completely substituted with a halogen atom, or can be partially substituted with a CN group or a NO 2 group. Can be substituted. R 3 to R 6 may form a cyclic structure, an aromatic ring structure, or a heterocyclic structure in cooperation with C 1 and / or C 2 atoms. Furthermore, R 2 and R 3 can also form a cyclic structure, an aromatic ring structure or a heterocyclic structure in cooperation with the C 1 and / or N atom. The carbon atoms contained in these substituents R 1 to R 6 are —O—, —C (O) —, —C (O) O—, —S—, —S (O) —, —SO 2 —. , -SO 3 -,-N =,-N = N-,-NH-,-NR '-,-N (R') 2 , -PR '-,-P (O) R'-,-P ( O) R'-O-, -OP (O) R'-O-, and -P (R ') 2 = N- can be substituted by atoms and / or groups selected from the group (where R 'Is an alkyl group having a C 1 to C 10 linear or side chain, or an alkyl group partially or fully substituted by an F atom, a saturated or partially or fully unsaturated cycloalkyl group , An unsubstituted or substituted phenyl group, or an unsubstituted or substituted heterocycle). X and Y each independently represent an S atom or an O atom. Furthermore, a dotted line shows a conjugate structure. ]
即ち、本発明は、「カチオン成分とアニオン成分とからなるイオン液体であって、前記カチオン成分が、前記一般式（１）で示され、前記一般式（１）中のＲ 1 およびＲ 2 の一方がメチル基であり、もう一方がエチル基またはプロピル基であり、Ｒ 3 〜Ｒ 6 がＨ原子であり、ＸおよびＹがＳ原子である有機物であり、かつ、前記アニオン成分が、（ＣＦ ３ ＳＯ ２ ） ２ Ｎ - 、ＰＦ ６ - またはＣ ２ Ｈ ５ ＳＯ ４ - のいずれかである、イオン液体」を提供することにより、前記目的を達成したものである。
That is, the present invention provides a ionic liquid consisting of a "cationic component and an anionic component, the cationic component, wherein is represented by the general formula (1), the general formula (1) R 1 and R 2 of One is a methyl group, the other is an ethyl group or a propyl group, R 3 to R 6 are H atoms, X and Y are S atoms, and the anion component is (CF 3 SO 2 ) 2 N − , PF 6 - or C 2 H 5 SO 4 - is either by providing an ionic liquid "is obtained by achieving the above object.
本発明によれば、良好な導電率を有し、低温からの広範な温度領域において安定した液体状態を保持するイオン液体を提供することができる。
本発明のイオン液体は、リチウム二次電池、電気二重層キャパシター、燃料電池、色素増感型太陽電池、または蓄電用デバイス向け電解質、添加剤、あるいは反応溶媒等に応用することができる。
According to the present invention, it is possible to provide an ionic liquid that has good conductivity and maintains a stable liquid state in a wide temperature range from a low temperature.
The ionic liquid of the present invention can be applied to electrolytes, additives, reaction solvents, and the like for lithium secondary batteries, electric double layer capacitors, fuel cells, dye-sensitized solar cells, or power storage devices.
本発明で用いられるカチオン成分は、前記一般式（１）で示されるものである。前記一般式（１）中の置換基Ｒ1 〜Ｒ6 は、Ｈ原子、C1〜C30 の直鎖状または側鎖を有するアルキル基、C2〜C30 の単一もしくは複数の二重結合を持つ直鎖状または側鎖を有するアルケニル基、C2〜C30 の単一もしくは複数の三重結合を持つ直鎖状または側鎖を有するアルキニル基、飽和状態または部分的にもしくは完全に不飽和状態のシクロアルキル基、アリール基、アルコキシアルキル基、複素環基のいずれかを示す。また、これらの置換基Ｒ1 〜Ｒ6 のうちの単一または複数の置換基に含まれるＨ原子は、ハロゲン原子によって部分的にもしくは完全に置換でき、あるいは、ＣＮ基、ＮＯ2 基によって部分的に置換できる。また、Ｒ3 〜Ｒ6 は、Ｃ1 および／またはＣ2 原子と共同して環状構造または芳香環構造または複素環構造を形成してもよい。更に、Ｒ2 およびＲ3 は、Ｃ1 および／またはＮ原子と共同して環状構造または芳香環構造または複素環構造を形成することもできる。これらの置換基Ｒ1 〜Ｒ6 に含まれる炭素原子は、-O-, -C(O)-,-C(O)O-,-S-,-S(O)-,-SO2-,-SO3-,-N=,-N=N-,-NH-,-NR'-,-N(R')2, -PR'-,-P(O)R'-,-P(O)R'-O-,-O-P(O)R'-O-,および-P(R')2=N-の群から選択される原子および／または原子団によって置換できる（ここで、R'はC1〜C10 の直鎖状または側鎖を有するアルキル基、またはＦ原子によって部分的もしくは完全に置換されたアルキル基、飽和状態または部分的にもしくは完全に不飽和状態のシクロアルキル基、非置換もしくは置換されたフェニル基、または非置換もしくは置換されたヘテロシクルスを示す。）前記一般式（１）中のＸおよびＹは、それぞれ独立して、Ｓ原子またはＯ原子を示す。更に、前記一般式（１）中の点線は、共役構造を示す。 The cationic component used in the present invention is represented by the general formula (1). Substituents R 1 to R 6 in the general formula (1) are H atoms, C 1 to C 30 linear or side chain alkyl groups, and C 2 to C 30 single or plural doubles. linear or alkenyl group having a side chain with binding, C 2 -C 30 single or multiple alkynyl group having a linear or branched having triple bonds, saturated state or partially or completely unsaturated A saturated cycloalkyl group, aryl group, alkoxyalkyl group, or heterocyclic group is shown. In addition, the H atom contained in one or a plurality of substituents among these substituents R 1 to R 6 can be partially or completely substituted with a halogen atom, or can be partially substituted with a CN group or a NO 2 group. Can be substituted. R 3 to R 6 may form a cyclic structure, an aromatic ring structure, or a heterocyclic structure in cooperation with C 1 and / or C 2 atoms. Furthermore, R 2 and R 3 can also form a cyclic structure, an aromatic ring structure or a heterocyclic structure in cooperation with the C 1 and / or N atom. The carbon atoms contained in these substituents R 1 to R 6 are —O—, —C (O) —, —C (O) O—, —S—, —S (O) —, —SO 2 —. , -SO 3 -,-N =,-N = N-,-NH-,-NR '-,-N (R') 2 , -PR '-,-P (O) R'-,-P ( O) R'-O-, -OP (O) R'-O-, and -P (R ') 2 = N- can be substituted by atoms and / or groups selected from the group (where R 'Is an alkyl group having a C 1 to C 10 linear or side chain, or an alkyl group partially or fully substituted by an F atom, a saturated or partially or fully unsaturated cycloalkyl group Represents an unsubstituted or substituted phenyl group, or an unsubstituted or substituted heterocycle.) X and Y in the general formula (1) each independently represent an S atom or an O atom. Furthermore, the dotted line in the said General formula (1) shows a conjugate structure.
本発明で用いられる前記アニオン成分は、 [RSO3] - , [Rf SO3]- ,[(Rf SO2)2N] - ,[(Rf SO2)3C] - ,[(FSO2)3C] - ,[RCH2OSO3] - ,[RC(O)O] - , [Rf C(O)O]- ,[CCl3C(O)O]- ,[(CN)3C] - ,[(CN)2CR]- , [(RO(O)C)2CR] - ,[R2P(O)O]- ,[RP(O)O2]2-,[(RO)2P(O)O] - , [(RO) P(O)O2]2- , [(RO)(R) P(O)O] - , [Rf 2P(O)O] - ,[R f P(O)O2]2- ,[B(OR)4] - ,[N(CF3)2]- ,[N(CN)2] - ,[AlCl4]- , PF6 - , BF4 - , SO4 2- ,HSO4 - ,NO3 - ,F- ,Cl - ,Br - , およびI - [式中の置換基Ｒは、Ｈ原子、ハロゲン原子、C1〜C10 の直鎖状または側鎖を有するアルキル基、C2〜C10 の単一もしくは複数の二重結合を持つ直鎖状または側鎖を有するアルケニル基、C2〜C10 の単一もしくは複数の三重結合を持つ直鎖状または側鎖を有するアルキニル基、飽和状態または部分的にもしくは完全に不飽和状態のシクロアルキル基のいずれかを示す。この置換基Ｒに含まれるＨ原子は、ハロゲン原子によって部分的にもしくは完全に、あるいは、ＣＮ基、ＮＯ2 基によって部分的に置換できる。また、この置換基Ｒに含まれる炭素原子は、-O- ，-C(O)-, -C(O)O-, -S-, -S(O)-, -SO 2 -, -SO 3 -, -N=, -N=N-, -NR'-, -N(R')2, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O-,および-P(R')2=N-の群から選択される原子および／または原子団によって置換できる（ここで、R'はC1〜C10 の直鎖状または側鎖を有するアルキル基、またはＦ原子によって部分的もしくは完全に置換されたアルキル基、飽和状態または部分的にもしくは完全に不飽和状態のシクロアルキル基、非置換もしくは置換されたフェニル基、または非置換もしくは置換されたヘテロシクルスを示す）。また、R f はフッ素含有置換基である。] の群の中から選ばれる一種または複数種が好ましい。 The anion component used in the present invention includes [RSO 3 ] − , [R f SO 3 ] − , [(R f SO 2 ) 2 N] − , [(R f SO 2 ) 3 C] − , [( FSO 2 ) 3 C] - , [RCH 2 OSO 3 ] - , [RC (O) O] - , [R f C (O) O] - , [CCl 3 C (O) O] - , [(CN ) 3 C] - , [(CN) 2 CR] - , [(RO (O) C) 2 CR] - , [R 2 P (O) O] - , [RP (O) O 2 ] 2- , [(RO) 2 P (O) O] - , [(RO) P (O) O 2 ] 2- , [(RO) (R) P (O) O] - , [R f 2 P (O) O] - , [R f P (O) O 2 ] 2- , [B (OR) 4 ] - , [N (CF 3 ) 2 ] - , [N (CN) 2 ] - , [AlCl 4 ] - , PF 6 − , BF 4 − , SO 4 2− , HSO 4 − , NO 3 − , F − , Cl − , Br − , and I − [wherein the substituent R is H atom, halogen atom, C alkyl group having a linear or side chain of 1 -C 10, alkenyl group having a linear or branched with single or multiple double bonds of C 2 -C 10, a single of C 2 -C 10 A straight-chain or side-chained alkynyl group with one or more triple bonds, either saturated or partially or fully unsaturated cycloalkyl group Show. The H atom contained in the substituent R can be partially or completely substituted by a halogen atom, or partially substituted by a CN group or NO 2 group. The carbon atom contained in the substituent R is -O-, -C (O)-, -C (O) O-, -S-, -S (O)-, -SO 2- , -SO 3- , -N =, -N = N-, -NR'-, -N (R ') 2 , -PR'-, -P (O) R'-, -P (O) R'-O- , -OP (O) R'-O-, and -P (R ') 2 = N- can be substituted by atoms and / or atomic groups (where R' is C 1 -C 10 A linear or side-chain alkyl group, or an alkyl group partially or fully substituted by an F atom, a saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted Represents a phenyl group, or an unsubstituted or substituted heterocycle). R f is a fluorine-containing substituent. ] One or more kinds selected from the group of
また、前記一般式（１）で示されるカチオン成分としては、前記一般式（１）中のＲ1 〜Ｒ6 が、それぞれＣ1 〜Ｃ6 の直鎖状または側鎖を有するアルキル基（Ｒ1 〜Ｒ6 は互いに同種でも異種であってもよい）であるものが好ましい。
また、前記一般式（１）中のＹは、Ｓ原子であることが好ましい。
As the cation component represented by the general formula (1), R 1 to R 6 in the general formula (1) are each an alkyl group having a linear or side chain of C 1 -C 6 (R 1 to R 6 may be the same or different from each other.
Further, Y in the general formula (1) is preferably an S atom.
また、前記一般式（１）の対イオンである前記アニオン成分が、 (ＣＦ3 ＳＯ2)2 Ｎ -、ＣＦ3 ＳＯ3 - 、ＣＦ3 ＣＯＯ- 、ＰＦ6 - 、ＢＦ4 - 、Ｎ (ＣＮ)2 - 、ＳＯ4 2- 、ＨＳＯ4 - 、ＮＯ3 - 、Ｆ- 、Ｃｌ- 、Ｂｒ- 、およびＩ- の群の中から選ばれる一種または複数種であり、かつ、前記一般式（１）中のＲ1 およびＲ2 が、それぞれＣ1 〜Ｃ6 の直鎖状または側鎖を有するアルキル基（Ｒ1 およびＲ2 は互いに同種でも異種であってもよい）であるものが好ましい。更に、Ｒ3 〜Ｒ6 がＨ原子であり、ＹがＳ原子であるイオン液体がより好ましい。 The anion component which is the counter ion of the general formula (1) is (CF 3 SO 2 ) 2 N − , CF 3 SO 3 − , CF 3 COO − , PF 6 − , BF 4 − , N (CN ) 2 − , SO 4 2− , HSO 4 − , NO 3 − , F − , Cl − , Br − , and I − , and the general formula (1) ) In which R 1 and R 2 are each an alkyl group having a linear or side chain of C 1 to C 6 (R 1 and R 2 may be the same or different from each other). Furthermore, an ionic liquid in which R 3 to R 6 are H atoms and Y is an S atom is more preferable.
また、前記一般式（１）中のＲ1 およびＲ2 の一方がメチル基であり、もう一方がエチル基またはプロピル基であり、Ｒ3 〜Ｒ6 がＨ原子であり、かつ、前記アニオン成分が（ＣＦ3 ＳＯ2)2 Ｎ -、ＰＦ6 - またはＢＦ4 - のいずれかであるイオン液体が特に好ましい。 In the general formula (1), one of R 1 and R 2 is a methyl group, the other is an ethyl group or a propyl group, R 3 to R 6 are H atoms, and the anion component An ionic liquid in which is (CF 3 SO 2 ) 2 N − , PF 6 − or BF 4 − is particularly preferable.
以上の本発明のイオン液体は、蓄電用デバイス向け電解質、電解液あるいは添加剤等に要求される良好な導電率を有する安定な液体であって、リチウム二次電池、電気二重層キャパシターあるいは色素増感型太陽電池に使用される材料として、また、各種反応に使用する反応溶媒として有用である。
なお、前記一般式（１）に示したカチオンは、便宜上Ｃ原子上に陽電荷を置いたメチルカチオン（メチリウム) として表しているが、ＸおよびＹで示されるヘテロ原子の種類によっては、陽電荷が分子内で非局在化しているものと考えられる。
The ionic liquid of the present invention described above is a stable liquid having good conductivity required for an electrolyte, an electrolytic solution or an additive for an electricity storage device, and is a lithium secondary battery, an electric double layer capacitor or a dye-enhanced liquid. It is useful as a material used for sensitive solar cells and as a reaction solvent used for various reactions.
In addition, although the cation shown in the general formula (1) is represented as a methyl cation (methylium) having a positive charge on the C atom for convenience, depending on the type of hetero atom represented by X and Y, the positive charge Is delocalized in the molecule.
前記一般式（１）で示されるカチオン成分を含むイオン液体の代表的な合成方法を下記に示す。 A typical method for synthesizing an ionic liquid containing the cation component represented by the general formula (1) is shown below.
原料となる前記一般式（２）または（３）で示される有機物に、アルキル化剤（Ｒ2 ＺまたはＲ1 Ｚ）を滴下し、所定の温度、時間、反応させる。ジエチルエーテル等で洗浄した後、真空乾燥する。アルキル化剤（Ｒ2 ＺまたはＲ1 Ｚ）としては、硫酸ジアルキルエステル、スルホン酸ジアルキルエステル、炭酸ジアルキルエステル、りん酸トリアルキルエステル、モノ−あるいはポリ−フルオロアルキルスルホン酸アルキルエステル、パーフルオロアルキルスルホン酸アルキルエステル、モノ−あるいはポリ−フルオロカルボン酸アルキル、パーフルオロカルボン酸アルキル、ヨウ化アルキル、臭化アルキル、塩化アルキル、硫酸、硝酸等を挙げることができる。 An alkylating agent (R 2 Z or R 1 Z) is added dropwise to the organic material represented by the general formula (2) or (3) as a raw material, and reacted for a predetermined temperature and time. After washing with diethyl ether or the like, vacuum drying is performed. Examples of the alkylating agent (R 2 Z or R 1 Z) include sulfuric acid dialkyl ester, sulfonic acid dialkyl ester, carbonic acid dialkyl ester, phosphoric acid trialkyl ester, mono- or poly-fluoroalkylsulfonic acid alkyl ester, perfluoroalkyl sulfone. Examples include alkyl alkyl esters, alkyl mono- or poly-fluorocarboxylates, alkyl perfluorocarboxylates, alkyl iodides, alkyl bromides, alkyl chlorides, sulfuric acid, and nitric acid.
また、例えば、下記の方法でアニオン交換することによって、異なるアニオンを有するイオン液体とすることも可能である。 Further, for example, ionic liquids having different anions can be obtained by anion exchange by the following method.
ここで、イオン結合性化合物ＡＱとしては、例えば、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 ，ＮａＮ（ＣＦ3 ＳＯ2 ）2 ，ＫＮ（ＣＦ3 ＳＯ2 ）2 ，ＣＦ3 ＳＯ3 Ｌｉ，ＣＦ3 ＳＯ3 Ｎａ，ＣＦ3 ＳＯ3 Ｋ，ＣＦ3 ＣＨ2 ＳＯ3 Ｌｉ，ＣＦ3 ＣＨ2 ＳＯ3 Ｎａ，ＣＦ3 ＣＨ2 ＳＯ3 Ｋ，ＣＦ3 ＣＯＯＬｉ，ＣＦ3 ＣＯＯＮａ，ＣＦ3 ＣＯＯＫ，ＬｉＰＦ6 ，ＮａＰＦ6 ，ＫＰＦ6 ，ＬｉＢＦ4 ，ＮａＢＦ4 ，ＫＢＦ4 ，ＬｉＳｂＦ6 ，ＮａＳｂＦ6 ，ＫＳｂＦ6 ，ＮａＮ（ＣＮ）2 ，ＡｇＮ（ＣＮ）2 ，Ｎａ2 ＳＯ4 ，Ｋ2 ＳＯ4 ，ＮａＮＯ3 ，ＫＮＯ3 等が挙げられるが、上記化合物に限られるものではない。 Here, examples of the ion-binding compound AQ include LiN (CF 3 SO 2 ) 2 , NaN (CF 3 SO 2 ) 2 , KN (CF 3 SO 2 ) 2 , CF 3 SO 3 Li, and CF 3 SO 3. Na, CF 3 SO 3 K, CF 3 CH 2 SO 3 Li, CF 3 CH 2 SO 3 Na, CF 3 CH 2 SO 3 K, CF 3 COOLi, CF 3 COONa, CF 3 COOK, LiPF 6, NaPF 6, KPF 6 , LiBF 4 , NaBF 4 , KBF 4 , LiSbF 6 , NaSbF 6 , KSbF 6 , NaN (CN) 2 , AgN (CN) 2 , Na 2 SO 4 , K 2 SO 4 , NaNO 3 , KNO 3 etc. Although it mentions, it is not restricted to the above-mentioned compound.
前記一般式（２）または前記一般式（３）中の置換基Ｒ1 〜Ｒ6 は、互いに独立しており、同一であっても異なっていても良い。置換基Ｒ1 〜Ｒ6 はそれぞれ、Ｈ原子、C1〜C30 の直鎖状または側鎖を有するアルキル基、C2〜C30 の単一もしくは複数の二重結合を持つ直鎖状または側鎖を有するアルケニル基、C2〜C30 の単一もしくは複数の三重結合を持つ直鎖状または側鎖を有するアルキニル基、飽和状態または部分的にもしくは完全に不飽和状態のシクロアルキル基、アリール基、アルコキシアルキル基、複素環基のいずれかを示す。また、これらの置換基Ｒ1 〜Ｒ6 のうちの単一または複数の置換基に含まれるＨ原子は、ハロゲン原子によって部分的にもしくは完全に置換でき、あるいは、ＣＮ基、ＮＯ2 基によって部分的に置換できる。また、Ｒ3 〜Ｒ6 は、Ｃ1 および／またはＣ2 原子と共同して環状構造または芳香環構造または複素環構造を形成してもよい。更に、Ｒ2 およびＲ3 は、Ｃ1 および／またはＮ原子と共同して環状構造または芳香環構造または複素環構造を形成することもできる。これらの置換基Ｒ1 〜Ｒ6 に含まれる炭素原子は、-O-, -C(O)-,-C(O)O-,-S-,-S(O)-,-SO2-,-SO3-,-N=,-N=N-,-NH-,-NR'-,-N(R')2, -PR'-,-P(O)R'-,-P(O)R'-O-,-O-P(O)R'-O-,および-P(R')2=N-の群から選択される原子および／または原子団によって置換できる（ここで、R'はC1〜C10 の直鎖状または側鎖を有するアルキル基、またはＦ原子によって部分的もしくは完全に置換されたアルキル基、飽和状態または部分的にもしくは完全に不飽和状態のシクロアルキル基、非置換もしくは置換されたフェニル基、または非置換もしくは置換されたヘテロシクルスを示す）。ＸおよびＹは、それぞれ独立して、Ｓ原子またはＯ原子を示す。更に、点線は、共役構造を示す。
上記のハロゲン原子としては、F, Cl, Br および Iを挙げることができる。
The substituents R 1 to R 6 in the general formula (2) or the general formula (3) are independent of each other and may be the same or different. Substituents R 1 to R 6 are each an H atom, a C 1 to C 30 straight chain or an alkyl group having a side chain, a C 2 to C 30 single chain or a straight chain having a plurality of double bonds, or An alkenyl group having a side chain, a linear or side chain alkynyl group having a C 2 to C 30 single or multiple triple bond, a saturated or partially or fully unsaturated cycloalkyl group, An aryl group, an alkoxyalkyl group, or a heterocyclic group is shown. In addition, the H atom contained in one or a plurality of substituents among these substituents R 1 to R 6 can be partially or completely substituted with a halogen atom, or can be partially substituted with a CN group or a NO 2 group. Can be substituted. R 3 to R 6 may form a cyclic structure, an aromatic ring structure, or a heterocyclic structure in cooperation with C 1 and / or C 2 atoms. Furthermore, R 2 and R 3 can also form a cyclic structure, an aromatic ring structure or a heterocyclic structure in cooperation with the C 1 and / or N atom. The carbon atoms contained in these substituents R 1 to R 6 are —O—, —C (O) —, —C (O) O—, —S—, —S (O) —, —SO 2 —. , -SO 3 -,-N =,-N = N-,-NH-,-NR '-,-N (R') 2 , -PR '-,-P (O) R'-,-P ( O) R'-O-, -OP (O) R'-O-, and -P (R ') 2 = N- can be substituted by atoms and / or groups selected from the group (where R 'Is an alkyl group having a C 1 to C 10 linear or side chain, or an alkyl group partially or fully substituted by an F atom, a saturated or partially or fully unsaturated cycloalkyl group , An unsubstituted or substituted phenyl group, or an unsubstituted or substituted heterocycle). X and Y each independently represent an S atom or an O atom. Furthermore, a dotted line shows a conjugate structure.
Examples of the halogen atom include F, Cl, Br and I.
上記のシクロアルキル基としてはシクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル等を挙げることができる。また、該シクロアルキル基は、シクロアルケニル基、シクロアルキニル基等の二重結合、三重結合等の不飽和結合を有するものも含み、またハロゲン原子によって部分的にもしくは完全に置換でき、あるいは、ＣＮ基、ＮＯ2 基によって部分的に置換できる。ハロゲン原子を１個または複数個有するアルキル基、アルケニル基、アルキニル基等不飽和結合を有するものも含む。 Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. The cycloalkyl group includes those having a double bond such as a cycloalkenyl group and a cycloalkynyl group, and an unsaturated bond such as a triple bond, and can be partially or completely substituted by a halogen atom, or CN It can be partially substituted by a group, NO 2 group. Also included are those having an unsaturated bond such as an alkyl group, alkenyl group, alkynyl group having one or more halogen atoms.
また、上記の複素環基としては、ピロジニル、ピロリニル、イミダゾリジニル、イミダゾリニル、ピラロゾリジニル、ピラゾニル、ピペリジル、ピペラジニル、モルホリニル、チエニル基等を挙げることができる。また、これらの複素環基にはアルキル基、アルコキシ基、水酸基、カルボキシル基、アミノ基、アルキルアミノ基、ジアルキルアミノ基、チオール基、アルキルチオ基並びにハロゲン原子を、一個または複数個含有していてもよい。 Examples of the heterocyclic group include pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrarozolidinyl, pyrazonyl, piperidyl, piperazinyl, morpholinyl, and thienyl groups. These heterocyclic groups may contain one or more alkyl groups, alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, alkylamino groups, dialkylamino groups, thiol groups, alkylthio groups, and halogen atoms. Good.
また、上記のアリール基としては、フェニル、クメニル、メシチル、トリル、キシリル基等を挙げることができる。また、これらのアリール基にはアルキル基、アルコキシ基、水酸基、カルボキシル基、アシル基、ホルミル基、アミノ基、アルキルアミノ基、ジアルキルアミノ基、チオール基、アルキルチオ基並びにハロゲン原子を、一個または複数個含有していてもよい。 Examples of the aryl group include phenyl, cumenyl, mesityl, tolyl, and xylyl groups. In addition, these aryl groups include one or more alkyl groups, alkoxy groups, hydroxyl groups, carboxyl groups, acyl groups, formyl groups, amino groups, alkylamino groups, dialkylamino groups, thiol groups, alkylthio groups, and halogen atoms. You may contain.
また、上記のアルコキシアルキル基としては、メトキシメチル、メトキシエチル、エトキシメチル、エトキシエチル基等を挙げることができる。また、これらのアルコキシアルキル基にはアシル基、アミノ基、アゾ基、チオ基、スルフォニル基、スルフィニル基、スルホナト基並びにハロゲン原子を、一個または複数個含有していてもよい。 Examples of the alkoxyalkyl group include methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups. Further, these alkoxyalkyl groups may contain one or a plurality of acyl groups, amino groups, azo groups, thio groups, sulfonyl groups, sulfinyl groups, sulfonate groups and halogen atoms.
さらにまた、式中のＸおよびＹで表されるヘテロ原子としては、ＳまたはＯ原子を挙げることができる。 Furthermore, S or O atom can be mentioned as a hetero atom represented by X and Y in a formula.
一方、前記一般式（１）の対イオンであるアニオン成分としては、（ＣＦ3 ＳＯ2)2 Ｎ -、ＣＦ3 ＳＯ3 - 、ＣＦ3 ＣＯＯ- 、ＰＦ6 - 、ＢＦ4 - 、Ｎ( ＣＮ)2 - 、ＳＯ4 2- 、ＨＳＯ4 - 、ＮＯ3 - 、Ｆ- 、Ｃｌ- 、Ｂｒ- 、Ｉ- 等を挙げることができる。また、該アニオン成分は複数種組み合わせることもできる。
イオン液体の分子量が大きくなると粘度が増し、導電率が低下する傾向にあるため、前記一般式（１）で示されるカチオンの分子量としては、３００以下が好ましく、より好ましくは２５０以下、さらに好ましくは２００以下である。
On the other hand, the anion component which is a counter ion of the general formula (1) includes (CF 3 SO 2 ) 2 N − , CF 3 SO 3 − , CF 3 COO − , PF 6 − , BF 4 − , N (CN ) 2 − , SO 4 2− , HSO 4 − , NO 3 − , F − , Cl − , Br − , I − and the like. In addition, a plurality of the anion components can be combined.
As the molecular weight of the ionic liquid increases, the viscosity tends to increase and the conductivity tends to decrease. Therefore, the molecular weight of the cation represented by the general formula (1) is preferably 300 or less, more preferably 250 or less, still more preferably 200 or less.
以下、本発明を実施例に基づき詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.
実施例１
(a) ３−エチル−２−（メチルチオ) −２−チアゾリウム硫酸エチルの調製
還流冷却管、滴下ロートおよび攪拌子を備えた三口丸底フラスコを窒素置換し、２−（メチルチオ) −２−チアゾリン 20.0g(150mmol)を入れ、撹拌しながら硫酸ジエチル34.7g(225mmol)を滴下した。窒素気流下で混合物を３０℃で７２時間攪拌し反応させ、うす黄色透明液体を得た。この液体をエーテルで充分に洗浄し、５０℃で５時間真空乾燥することにより、41.0g(収率９５％) の３−エチル−２−（メチルチオ) −２−チアゾリウム硫酸エチルを得た。
化合物の同定は核磁気共鳴分析装置(BRUKER 社製 BRUKER Ultra Shield 300 NMR Spectrometer)で行なった。スペクトルデータを以下に示す。
1H- NMR(300MHz, 溶媒:acetone-d6, 標準物質: テトラメチルシラン)
δ 4.77(t, 2H)
4.01-3.84(m, 6H)
3.01(s, 3H)
1.42(t, 3H)
1.15(t, 3H)
以下に構造式を示す（式中の点線は、共役構造を示す）。
Example 1
(a) Preparation of ethyl 3-ethyl-2- (methylthio) -2-thiazolium sulfate A three-necked round bottom flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen, and 2- (methylthio) -2-thiazoline 20.0 g (150 mmol) was added, and 34.7 g (225 mmol) of diethyl sulfate was added dropwise with stirring. The mixture was stirred and reacted at 30 ° C. for 72 hours under a nitrogen stream to obtain a pale yellow transparent liquid. This liquid was thoroughly washed with ether and vacuum-dried at 50 ° C. for 5 hours to obtain 41.0 g (yield 95%) of ethyl 3-ethyl-2- (methylthio) -2-thiazolium sulfate.
The compound was identified using a nuclear magnetic resonance analyzer (BRUKER Ultra Shield 300 NMR Spectrometer manufactured by BRUKER). The spectrum data is shown below.
1 H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane)
δ 4.77 (t, 2H)
4.01-3.84 (m, 6H)
3.01 (s, 3H)
1.42 (t, 3H)
1.15 (t, 3H)
The structural formula is shown below (the dotted line in the formula indicates a conjugated structure).
(b) ３−エチル−２−（メチルチオ) −２−チアゾリウムビストリフルオロメタンスルフォニウムイミドの調製
(a) で得られた３−エチル−２−（メチルチオ) −２−チアゾリウム硫酸エチル28.7g(100.0mmol)を純水200ml に溶解し、この水溶液中に、リチウムビストリフルオロメタンスルフォニルイミド 28.7g(100.0mmol) を純水200ml に溶解した水溶液を、攪拌しながら加えた。６０分間攪拌を続け、反応させて疎水性のうす黄色の透明な液体を得た。得られた疎水性液体を純水で２〜３回洗浄後、ジクロロメタンで抽出した。アルミナカラムで精製し、無色透明な液体とした。その液体を濃縮した後、８０℃で１０時間真空乾燥することにより、室温で無色透明な液体を39.8g(収率９０％) 得た。
化合物の同定は核磁気共鳴分析装置 (BRUKER社製 BRUKER Ultra Shield 300 NMR Spectrometer)で行い、目的物である３−エチル−２−（メチルチオ) −２−チアゾリウムビストリフルオロメタンスルフォニルイミドであることを確認した。スペクトルデータを以下に示す。
1H- NMR(300MHz, 溶媒: acetone-d6, 標準物質: テトラメチルシラン)
δ 4.75(t, 2H)
3.99-3.90(m, 4H)
3.01(s, 3H)
1.42(t, 3H)
19F-NMR(282MHz, 溶媒: acetone-d6, 標準物質:CF3Cl)
δ -79.87(s, 6F)
以下に構造式を示す（式中の点線は、共役構造を示す）。
(b) Preparation of 3-ethyl-2- (methylthio) -2-thiazolium bistrifluoromethanesulfonium imide
28.7 g (100.0 mmol) of ethyl 3-ethyl-2- (methylthio) -2-thiazolium sulfate obtained in (a) was dissolved in 200 ml of pure water, and 28.7 g of lithium bistrifluoromethanesulfonylimide ( An aqueous solution in which 100.0 mmol) was dissolved in 200 ml of pure water was added with stirring. Stirring was continued for 60 minutes and allowed to react to obtain a hydrophobic light yellow transparent liquid. The obtained hydrophobic liquid was washed 2-3 times with pure water and extracted with dichloromethane. Purification with an alumina column gave a colorless and transparent liquid. The liquid was concentrated and then vacuum dried at 80 ° C. for 10 hours to obtain 39.8 g (yield 90%) of a colorless and transparent liquid at room temperature.
The compound was identified with a nuclear magnetic resonance analyzer (BRUKER Ultra Shield 300 NMR Spectrometer manufactured by BRUKER) and the target product was 3-ethyl-2- (methylthio) -2-thiazolium bistrifluoromethanesulfonylimide. It was confirmed. The spectrum data is shown below.
1 H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane)
δ 4.75 (t, 2H)
3.99-3.90 (m, 4H)
3.01 (s, 3H)
1.42 (t, 3H)
19 F-NMR (282 MHz, solvent: acetone-d6, standard: CF 3 Cl)
δ -79.87 (s, 6F)
The structural formula is shown below (the dotted line in the formula indicates a conjugated structure).
走査型示差熱量計( 島津製作所( 製)DSC8230) による融点測定を行った。融点は２０．４℃、結晶化温度は５．０℃であった。また、交流インピーダンス法（北斗電工（株）製電気化学測定システムＨＺ−３０００）による２５℃における導電率は０．３３Sm-1であった。 The melting point was measured with a scanning differential calorimeter (DSC8230, manufactured by Shimadzu Corporation). The melting point was 20.4 ° C and the crystallization temperature was 5.0 ° C. Moreover, the electrical conductivity in 25 degreeC by the alternating current impedance method (Hokuto Denko Co., Ltd. electrochemical measurement system HZ-3000) was 0.33 Sm- 1 .
(c) ３−エチル−２−（メチルチオ) −２−チアゾリウムヘキサフルオロホスフェートの調製
(a) で得られた３−エチル−２−（メチルチオ) −２−チアゾリウム硫酸エチル4.31g(15mmol) を純水100ml に溶解し、この水溶液中に、LiPF6 2.28g(15mmol) を純水100ml に溶解した水溶液を、攪拌しながら加えた。６０分間攪拌を続け、反応させて疎水性の紫色の固体を得た。得られた疎水性固体を純水で２〜３回洗浄後、ジクロロメタンで抽出した。アルミナカラムで精製し、抽出液を濃縮した後、８０℃で１０時間真空乾燥することにより、２５℃において白色固体の化合物を2.9g（収率６４％）得た。
化合物の同定は核磁気共鳴分析装置 (BRUKER社製 BRUKER Ultra Shield 300 NMR Spectrometer)で行い、目的物である３−エチル−２−（メチルチオ) −２−チアゾリウムヘキサフルオロホスフェートであることを確認した。スペクトルデータを以下に示す。
1H- NMR(300MHz, 溶媒: acetone-d6, 標準物質: テトラメチルシラン)
δ 4.72(t, 2H)
3.97-3.89(m, 4H)
3.01(s, 3H)
1.42(t, 3H)
19F-NMR(282MHz, 溶媒: acetone-d6, 標準物質:CF3Cl)
δ -71.23 (s, 3F)
-73.74 (s, 3F)
以下に構造式を示す（式中の点線は、共役構造を示す）。
(c) Preparation of 3-ethyl-2- (methylthio) -2-thiazolium hexafluorophosphate
4.31 g (15 mmol) of ethyl 3-ethyl-2- (methylthio) -2-thiazolium sulfate obtained in (a) was dissolved in 100 ml of pure water, and 2.28 g (15 mmol) of LiPF 6 was dissolved in pure water. An aqueous solution dissolved in 100 ml was added with stirring. Stirring was continued for 60 minutes and allowed to react to obtain a hydrophobic purple solid. The obtained hydrophobic solid was washed 2-3 times with pure water and then extracted with dichloromethane. After purification with an alumina column and concentration of the extract, vacuum drying was performed at 80 ° C. for 10 hours to obtain 2.9 g (yield: 64%) of a white solid compound at 25 ° C.
The compound was identified by a nuclear magnetic resonance analyzer (BRUKER Ultra Shield 300 NMR Spectrometer manufactured by BRUKER) and confirmed to be the target product, 3-ethyl-2- (methylthio) -2-thiazolium hexafluorophosphate. did. The spectrum data is shown below.
1 H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane)
δ 4.72 (t, 2H)
3.97-3.89 (m, 4H)
3.01 (s, 3H)
1.42 (t, 3H)
19 F-NMR (282 MHz, solvent: acetone-d6, standard: CF 3 Cl)
δ -71.23 (s, 3F)
-73.74 (s, 3F)
The structural formula is shown below (the dotted line in the formula indicates a conjugated structure).
走査型示差熱量計( 島津製作所( 製)DSC8230) による融点測定を行った。融点は５７．０℃、結晶化温度は３２．０℃であった。
The melting point was measured with a scanning differential calorimeter (DSC8230, manufactured by Shimadzu Corporation). The melting point was 57.0 ° C., and the crystallization temperature was 32.0 ° C.
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