TWI286547B - Ionic molten salt and method of producing the same - Google Patents

Abstract

A novel ionic molten salt of the structure: wherein R1 is selected from the group consisting of -(CH2)x- and the linear or branched isomers thereof, wherein x is 1 to 10; R2 is selected from -(CH2)pH and the isomers thereof; p is 1 to 20; A is an organic or inorganic anionic moiety and selected from the group consisting of R3CO2-, BF4, and PF6; and R3 is an alkyl group having 1 to 3 carbon atoms, phenyl, naphthyl, biphenyl, an aliphatic fluorocarbon group, or an aromatic fluorocarbon group.

Description

i 1286547 玖, invention description: [Technical field of the invention] The present invention relates to a novel ion salt (Ionic molten salt) and a preparation method thereof, and more particularly to a method comprising simultaneously containing pyridinium and yttrium An ionic solution of two positive ion groups of the gun (Imidazolium). [Prior Art] An ionic liquid is also called a molten salt, and its general structure is composed of an organic positive ion and an inorganic negative ion group. A combination of the above two kinds of positive and negative ions can give a plurality of compounds having different melting point ranges. Ion solutions have received much attention in recent years because of their following characteristics: 1. A wide range of solvent properties for organic or inorganic compounds; 2. High polarity properties, which can be called non-aqueous solutions of polar solvents; Some are not miscible with organic solvents and aqueous solutions; 4. Low volatility, low-vacuum method can be used to remove impurities; 5. Compared with general solvents, it has the advantages of low flame resistance and high heat resistance. Due to the above characteristics, ionic melts have been applied to electrolytes, solvents, and catalysts. For the control of the heat and the control of the bright spot, the currently widely used organic cation compounds are derivatives of Imidazole and pyridine. There is a fairly detailed report in the recently published Chem. Review, 1999, 99, 2071 "Room-temperature Ionic liquids: solvents for synthesis and catalysis." U.S. Patent Nos. 5,827,602 (1998) and 6,025,457 (2000). The chemical structure of the ionic melts disclosed in the year is a single pyridine or imidazole cation group. The RG Reddy et al. (ASME Proceedings of Solar Forum 2001, Washington DC, April 21-25, 2001) It is reported that changing the negative ion group can greatly reduce the modification date of the patent specification of 12865^7 132421. Revision date: 93.10.18 .: , the melting point of low ionic melt, for example: ethyl oxime taste ° sitting • hexafluoride The melting point temperature (Tm) of 粦(Ethylmethylimidazolium·PF6)=60°C, but ethylmethyl sulphate. The acetate group is 1:]171111^1; 113^1111(132〇1]^111*^/ ^〇〇〇) The melting point temperature (Tm) = -45QC, the melting point temperature difference between the two can reach 100 ° C or more. In addition, R·G·Reddy et al. also found that the use of different types of positive ion groups and An ionic melt of an anion group, An ionic melt mixture with optimum melting point and heat resistance, for example: 50% butylmethylimidazolium BF4 (Butylmethylimidazolium BF4) (thermal cracking temperature Tdee=407QC) and 50% hexylmethylimidazole•double- [(Trifluoromethylsulfonyl)imide] [Hexylmethylimidazolium bis(trifluoromethylsulfonyl) imide (NTf2)] (thermal cracking temperature Tdee=341°C) to obtain a higher thermal cracking temperature of the ionic melt mixture (thermal cracking temperature) Tdec^427QC). This mixed ion melt is currently being used as a thermal energy storage medium for solar thermal energy systems. Also by R. Hagiwara et al.: J. 〇f Fluorine Chem·, No. 105, p. 221 (2000), also mentioned the incorporation of two different ionic melts, which can give new functional properties of new ionic solutions' and lower temperature eutectic points, but according to our experience, different The ratio of imidazolium BF4 (imidazolium BF4) and pyridinium BF4 (pyridinium BF4) are mixed as ionic melts. In practice, some phase separation of two ionic solutions occurs. Yau Valley phenomenon is easy to sacrifice visual concept that is to be, it should lead to anti-unstable environment changes. Since the melting point of the ionic melt of the imidazole or pyridine alone is limited by the limited kinds of alkyl substituents attached to the side, the ability to adjust the melting point or solvent properties is also very high. limited. In addition, the imidazolyl group and the alkyl substituent of the pyridyl group also occupy a considerable space for the compound. Furthermore, it is known that the chemical structure of an ionic melt of an aromatic amine salt is 1286547 h ί * , and the ionic group contains only a chemical group of -imidazole or pyridine. In order to change the melting point of the salt, in addition to changing the kind of the negative ion group, it is necessary to bond the positive ion group structure with a different melting point group or an asymmetric side chain group to obtain the effect of changing or lowering the melting point. However, the large asymmetric side chain groups also increase the volume of the ionic melt, thereby causing a decrease in ion concentration characteristics per unit volume. This report can be found in the paper by P_ Bonhote et al.: inorg. Chem, No. 35, p. 1168 (1996) and R. Hagiwara et al.: j. 〇mu〇rine chem., No. 105, 221 Page (2000) is shown. SUMMARY OF THE INVENTION In view of this, the present invention provides an imidazole gun and a pyridine gun simultaneously placed on the same compound by a method of generally copolymerizing a compound, such that the ratio of imidazole and pyridine does not change with the environment, and The compound has a relatively large asymmetric molecular structure, and together with the use of the alkyl compound, the ion density per unit volume is greatly increased, and the space occupied by the alkyl group is reduced. The novel ionomers combine the properties of both imidazole and pyridine groups to extend the use of ionic melts for solutions, electrolytes and catalytic reactions reported in the prior art. For example, as an ionic reagent. The reaction medium or solvent and the electrolyte of the energy storage battery. In order to attain the present invention, the method for preparing an ionic melt of the present invention comprises the steps of: (a) reacting pyridine with alkane or an ether compound having a substituent B (compound u to obtain compound II;

B-R1-B Compound I

Compound II 128654 Print 132421 Patent Specification Revision Page Revision 94:8.4 (b) Purification of Compound II with the Substituted R2 Sodium (Compound 111)

Γ \ R2 compound III is reacted to obtain an alkane or ether compound IV containing imidaz〇Hum salts and PyHdinium salts;

And (c) reacting the compound IV with an organic or inorganic metal compound MA to obtain an ionic melt as shown by the compound V. (Package " "Miao," 2,

Compound V Alternatively, another method of preparing an ionic melt of the present invention comprises: (a) reacting an imidazole having a substituent R2 (compound 111) with an alkane or ether compound having a substituent B to obtain a compound VI;

Compound VI (b) is purified from compound VI and reacted with pyridinium to obtain a burned or etherated compound IV containing imidazolium salts and pyridinium salts; and (c) compound IV with an organic or inorganic metal The compound Μ A is reacted to obtain an ionic solution such as the compound 0424-733 lTWF4; 02900040; Phoebe 9 1286547. The alkane or ether compound having the substituent B of the above method (the compound 〇' Ri is -(CH2)x- or -(CH2[-〇-(CH2)y]Z-, wherein B is the same or different teeth The prime is selected from F, a, Br, I and 〇S03R4, and the fork is i~1〇, 丫 is i~4, z is 1~1〇〇〇, and the organic or inorganic metal compound μα is rc 〇2M, RS03M, MBF4, MPF6 or MCF3s〇3, wherein M is selected from Ag, Li, H or NH4, and R2 is a burnt group, an aromatic group or the corresponding gas-based substituents. In the imidazole having a substituent & immortal, the rule 2 is _(〇112)1)11 or an isomer thereof, wherein p is from 1 to 20. Further, the novel ionic melt of the present invention has the following structure: ((^ N-Ri-disgrace,

2A Θ where H(CH2)X... Qing 2[_〇仰咖(四)和料(四) should be a linear or branched isomer of a compound, where \ is (a) ❹巧为i~4, z is L·, and R2 is - (CH2) pH and an isomer of the compound, wherein p is i~2Q; A is an organic or inorganic anion group. Specifically, the above formula t "R3C02_, R3S03-, is a calcined m mn compound having a carbon number of 1 to 3 or a scented fluorocarbon. The ion (IV) provided according to the present invention has a positive ion group containing (4) and D has two advantages over the two groups: 1. The asymmetry increases, and the salt m is more effectively changed. 2. The ion characteristics in the early volume are relatively increased, and the application surface is enlarged; 3. This salt can simultaneously Contains two different anionic groups, relatively effective to change 0424-733 lTWF4; 02900040; Phoeb< 10 1286547 to change its melting point range; 4. It has a mixed effect of simultaneously containing miso salt and 吼° fixed salt, but can avoid The phase separation is caused by the mixing of the imidazolium salt and the pyridinium salt. [Embodiment] In order to make the above objects, features and advantages of the present invention more apparent, the preferred embodiments are illustrated below, The details are as follows: EXAMPLES Example 1. (1) Synthesis of Compound II Dibromopropene (1.01 g, 5.0 mmol) was placed in a reaction flask, and D was bitten at room temperature. .43g, 5_5mmol), after two hours, the solid slowly precipitated and was searched overnight ( Approximately 1 Ohr) 'Add solids to the scrape' to the acetone and mix for 30 minutes, quickly filter, and wash the solids with acetone, then quickly collect the solids in the reaction flask (solids will quickly in the air) Deliquescent), drained in a vacuum pump. Compound II with melting point = 138 °C is obtained. The reaction formula is as follows:

Compound II was measured by nuclear resonance (NMR) and far infrared (IR) with the following data: 1H NMR (400 MHz 5 D2 〇 / DMSO / ppm): 8.94 (d, 2H), 8.62 (t, 1H), 8.15 (t, 2H), 4.81 (t, 2H), 3-49 (t, 2H), 2.60 (m, 2H) IR: 3054, 2964, 1643, 1488, 1178, 775, 683 cm·1 (2) Compound IV (negative ion) Synthesis of Br-) (made by compound II) 0424-733 lTWF4; 02900040; Phoebe 11 1286547 "Filling, _ h Compound II (1.Og, 3.59mmol) with 5ml of methyl alcohol as solution, and Λ

Base - microphone. Sit (〇.35g, 4.30mmol), mix for 8hr, add appropriate amount of acetone and mix for 30 minutes, then let the ice bath for 10 minutes, quickly filter (the solid will quickly deliquesce in the air), then acetone (2 ml The solid is washed, and then the solid is quickly collected in a reaction flask and drained in a vacuum pump to obtain a compound IV having the following reaction formula.

rN-CH2CH2CH2Br

I-ch3

. The compound IV had a melting point of 144 °C. Compound IV was measured by nuclear resonance (NMR) and far infrared (IR) with the following data: 1H NMR (400 MHz? D20/DMS0-d6/ppm): 8.87 (d5 2H); 8.45 (t? 1H); 7.97 (t , 2H); 7.34 (m, 3H); 4.60 (t, 2H); 4.26 (t, 2H); 3.76 (s, 3H); 2.53 (m? 2H). IR: 3086, 1635, 1576, 1489, 1170 , 773, 683 cnT1 (3) Reaction of BFr in place of Bf (synthesis of compound V (negative ion is BFD): Compound IV was placed in a reaction flask, MeOH was added, and then an excess (3 equivalents of mole) of AgBF4 was added for 3 days. After filtration, the solution was drained, centrifuged with ethanol, and the by-product of the salt was separated to obtain an ionic melt (compound V) having a negative ion group of BFr. Melting point = 93 ° C. 0424-733 lTWF4; 02900040; Phoebe 12 1286547

The compound v was measured by nuclear resonance (NMR) and far infrared (IR). The data is as follows: iHNMR (400 MHz, D20/DMS0-d6/ppm): 8.87 (d, 2H); 8.76 (s 1H) 8.61 (t, 1H) 8.13(t,2H); 7.50(m,2H); 4.74(t,2H); 4.4l(t,2h): 3.92(s? 3H); 2.68(m? 2H). 5 IR: 3159, 2986, 1635, 1580, 1490, 1219cm·1 (4) Reaction of PF plant in place of Bf (Synthesis of compound VII (negative ion is used as an excess (3 equivalents of molar) of AgPF6. Compound IV was placed in a reaction flask and MeOH was added. Then, AgPF6 was added (3 equivalents of mole) for 3 days. After filtration, the solution was drained, and the product was separated by centrifugation with ethanol to obtain a salt by-product, and an ion having a negative ion group of PFr (compound VII) was obtained. Melting point = 126 ° C.

The compound VII was measured by a nuclear resonance (NMR) and far infrared (IR) data as follows: !HNMR (400 MHz, D20/DMS0-d6/ppm) ·· 9.08 (d, 2H); 8.12 (S, 1H), 8.31(t,1H); 8.00(t,2H); 7.41(m,2H); 4.70(t,2H); 4.24(t,2H); 3.84(s,3H); 2.49(m,2H). IR (KBr): 3435, 3174, 3124, 1673, 1581, 1566, 1492, 1457, 1436, 1353, 1174, 1113, 835, 624, 558 cm.1

Theoretical value of elemental analysis: C12H17F12N3P2 (493.07): C 29·22; H 3.47; N 0424-733 lTWF4; 02900040; Phoebe 13 I

Replacing Br-reaction (synthesis of compound VIII (negative ion b 1286547 8·52·experimental value C 29.32; H3.96; N8.59%·(5) PF6-—)) using a small amount (0.5 equivalent mol) of AgPF6 Compound IV was placed in a reaction flask, MeOH was added, followed by addition of human hydrazine (0.5 eq. mol) of AgPF6 for 3 days. After filtration, the solution was drained. The alcohol by centrifugation was carried out to separate the salt by-product. An ion having a negative ion group of pFr and a solution (Compound VIII) were obtained. Melting point = 110 ° C.

Compound VIII was measured by nuclear resonance (NMR) and far infrared (IR) with the following data: iNMR (400 MHz, D20/DMS0-d6/ppm): 9.00 (d, 2H);, 8·31 (ιη, 4H) 7.41(m,2H); 4.50(t,2H); 4.24(m,2H); 3.84(m,3H); 2.49(m,2H). IR(KBr) : 3435, 3174, 1663, 1581,1566 , 1490, 1436, 1174, 1113, 829, 674, 558 cm·1 Example 2. Synthesis of Compound V (negative ion is CF3COO-) Steps (1) and (2) are the same as in Example 1, except for (3) Step, replacing BF4 in Example 1 with CF3COCT: Add AgOCOCF3 (2 eq) to the RO aqueous solution of Compound IV, and then put it into the oil pan preheated at 70 ° C, and filter most of the solids after three hours of reaction. After diluting the filtrate with RO water, it was centrifuged to obtain a clear liquid, followed by concentration and drying to obtain a product. An ion melt (compound V) having an anion group (A) of CF3COO was obtained. Melting point = 18 ° C.

The compound V 14 0424-733 lTWF4; 02900040; Ph〇ebe 1286547 IR: 3090, 1794, 1694, 1578, 1493, 1200 cm-1 Elemental analysis: C16H17F6N304 Molecular weight: 429.31 was measured by nuclear resonance (NMR) and far infrared (IR). Theoretical value C 44·76%; N 9.7%; F 26.55% Experimental value C44.1%; N 9.5%, F 26.9% Example 3. (1) Synthesis of compound VI Dibromopropane (2.02 g, 10 mmol) Put in a reaction flask, slowly add N-methyl-imidazole (0.90 g, llmmol) at room temperature, stir for 12 hours, precipitate a solid, add the reaction flask to acetone and stir for 30 minutes, quickly filter, then The solid was washed with acetone and then drained in a vacuum pump. Compound VI is available. Melting point = 149 °C.

Compound VI was measured by nuclear resonance (NMR) and far infrared (IR) with the following data: iHNMR (200 MHz, D20/DMS0_d6/ppm): 8_81 (s, 1H), 7.55 (m, 2H); 4.41 (m, 3.H (3,3H); (Prepared by compound VI) Compound VI (1.42g, 5.0mmol) was dissolved in 5ml of methanol, added D to 13 (0.47g, 6.0mmol), stirred for 14hr, then added with appropriate amount of acetone for 30 minutes to wash, then static After ice-cold bath for 20 minutes, it was quickly filtered, and then the solid was washed with acetone (5 ml), then the solid was collected in a reaction flask and drained in a vacuum pump to obtain Compound IV, which had the same 1H NMR data as in Example 1. The melting points of the prepared compounds II, IV, V, VI, VII and VIII are listed in the following table: 丨爹正1286547 I Replenish the teeth and then collect the solid in the reaction flask, IV in the vacuum pump, 1H NMR data and Example 1 The melting points of the above-prepared compounds II, IV, V, VI, VII and VIII are listed in the following table: Compound species melting point Tm (°C) Compound II 138 Compound IV (negative ion is Br~") 144 Compound V (negative ion is CF3COO-) 18 Compound VI 149 Compound V (negative ion is BF〇93 Compound VII (negative ion is PF") 126 Compound VIII (negative ion is PFr) And the present invention has been disclosed in the above preferred embodiments. However, it is not intended to limit the invention, and those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention is defined by the scope of the appended patent application. 0424-733 lTWF4; 02900040; Phoebe 16 1286547 [Simple description] None. [Symbol description] None 0

Claims (1)

Repair: Erff s τ94τθ^. I286Wi 32421 application for the scope of patent amendments, the scope of patent application: Panzi melt, its structure is as follows: Wherein 1 is -(«12)^, wherein X is an integer from 1 to 10; R2 is (^ to c3 alkyl; two A are the same or different organic or inorganic compounds, and A· is R3C02_, bf4_, or Pf6_, wherein r3 is q~C3 alkyl or CF3. 2. A method of preparing an ionic melt according to claim 1, which comprises: (a) a pyridine and a substituted alkyl group The compound is reacted to obtain a compound II; Compound II wherein the alkyl compound having the substituent B has the chemical formula B_(CH2)XB, wherein each B is the same or different halogen, and is selected from the group consisting of F, C, Br, and I, and X is 1 ~10, and Ri is -(«12) wide; (b) Purification of compound II with imidazole with substituent R2 (compound III) 1%^N~R2 Compound III is reacted to obtain a pyroline compound IV containing imidazolium salts and pyridinium salts; 0424-733 lTWF4; 02900040; Phoebe 18 1286547 Wherein R2 is a Ci~C3 alkyl group and each B is the same or different; and (C) reacting the compound IV with an organic or inorganic metal compound MA to obtain an ion-refining body represented by the chemical formula ν Compound V wherein the organic or inorganic metal compound is selected from the group consisting of r3c〇2M, MBF4, and MPF6, wherein the μ system is selected from the group consisting of Ag, Li, Na, and K, and r2 is Cl. ~C3 alkyl, & Cl~c3 alkane or cf3. 3. A method of preparing an ionic melt according to claim 1, which comprises: (a) an imidazole having a substituent r2 (Compound 11; [) Compound III is reacted with an alkane compound having a substituent B to obtain a compound VI; Compound VI wherein the alkyl compound having the substituent B has the chemical formula B_(CH2)x_B, wherein 0424-733 lTWF4; 02900040; Phoebe 19 1286547 each B is the same or different halogen, selected from F, C, Br, and A group consisting of I, X is 1 to 10, and I is -(«12)^, and R2 is (^~(33 alkyl; (b) the compound VI is purified and reacted with pyridine to obtain an imidazole salt ( Imidazolium salts) and pyrophoric pyridinium salts of pyrophoric compounds IV; a 2B and (c) reacting the compound IV with an organic or inorganic metal compound A to obtain an ionic melt as shown in the chemical formula V. Compound V wherein the organic or inorganic metal compound MA is selected from the group consisting of R3C02M, MBF4, and MPF6, wherein the lanthanide is selected from the group consisting of Ag, Li, Na, and K, and R2 is Ci~C3. Alkyl, R3 is a <^~03 alkane or CF3. 0424-733 lTWF4; 02900040; Phoebe 20