CN103408496B - A kind of two imidazole type ionic crystal and preparation method thereof - Google Patents

A kind of two imidazole type ionic crystal and preparation method thereof Download PDF

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CN103408496B
CN103408496B CN201310319862.6A CN201310319862A CN103408496B CN 103408496 B CN103408496 B CN 103408496B CN 201310319862 A CN201310319862 A CN 201310319862A CN 103408496 B CN103408496 B CN 103408496B
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imidazole type
ionic crystal
filtrate
type ionic
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CN103408496A (en
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赵杰
丛姗
邹贵付
曹梦瑜
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Suzhou University
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Suzhou University
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Abstract

The present invention relates to a kind of two imidazole type ionic crystal, its chemical structure of general formula is: or , wherein: X is the one in Cl, Br, I, Y is BF 4, TFSI, PF 6in one, q is the integer of 0 to 5.Two imidazole type ionic crystals of the present invention's synthesis, relative to single imidazole type ionic crystal, it has higher specific conductivity (~ 10 -5s/cm), and the method preparing this pair of imidazole type ionic crystal is simple to operate, is conducive to commercially producing, has a extensive future.

Description

A kind of two imidazole type ionic crystal and preparation method thereof
Technical field
The present invention relates to a kind of ionic crystal, be specifically related to a kind of two imidazole type ionic crystal and preparation method thereof.
Background technology
Ionic crystal is combined by positive and negative ion the crystal formed by a certain percentage by ionic linkage, and conventional ionic crystal is such as NaCl, CaCl 2and so on inorganic salt.Along with organic synthesis mechanism, the deepening continuously and develop of technology, increasing organic ionic crystal just is constantly synthesized out, has enriched kind and the definition of ionic crystal, has widened its Application Areas.
Because organic ionic crystal has thermally-stabilised good, specific conductivity is high, do not leak in solid etc. advantage, they are as a kind of composition of solid electrolyte or accurate solid electrolyte, be widely used in solar cell, ultracapacitor, lithium ion battery equal energy source device, can overcome the shortcomings such as liquid electrolyte easy firing leaks, volatile, difficult encapsulation, high toxicity, poor stability, therefore organic ionic crystal causes the extensive concern of scientific worker just gradually.
Publication number is that the Chinese invention patent of CN 102592832A discloses a kind of single imidazole type ionic crystal, and uses it for and prepare solar cell solid state electrolyte.But this single imidazole type ionic crystal specific conductivity is lower, is approximately 1 × 10 -6s/cm, the solid state electrolyte utilizing this single imidazole type ionic crystal to prepare is applied in dye sensitization solar battery the electricity conversion that can only reach 4.45%.Therefore the ionic crystal that necessary synthesis is novel, improves its specific conductivity, thus improves the energy device performance containing this ionic crystal, constantly advances towards industrialization direction.
Summary of the invention
The object of the invention is to provide a kind of two imidazole type ionic crystals with high conductance to overcome the deficiencies in the prior art.
For solving above technical problem, a kind of technical scheme that the present invention takes is: a kind of two imidazole type ionic crystal, is characterized in that: its chemical structure of general formula is:
Wherein: X is the one in Cl, Br, I, q is the integer of 0 to 5.
Optimally, described X replaces with Y, and wherein Y is BF 4, TFSI, PF 6in one.
The present invention also provides the preparation method of a kind of pair of imidazole type ionic crystal, and it comprises the following steps:
(1) add successively in reaction vessel acetone, , , K 2cO 3, 60 ~ 80 DEG C, under protection of inert gas, react and filter to get filtrate after 10 ~ 15 hours, filtrate obtains product a through rotary evaporation, sherwood oil recrystallization;
(2) add successively in another reaction vessel acetonitrile, , imidazoles, KOH, filter to get filtrate after at room temperature reacting 10 ~ 20 hours, filtrate obtains product b through rotary evaporation, deionized water recrystallization;
(3) be added drop-wise to by product a in the acetone soln of product b, condensing reflux reaction 10 ~ 15 hours at 30 ~ 50 DEG C, rotary evaporation removing acetone, repeatedly washs with ethyl acetate and ether respectively, obtains product c after drying;
(4) product c is dissolved in acetonitrile, adds , KOH, filter to get filtrate after at room temperature reacting 10 ~ 20 hours, rotary evaporation removing acetonitrile, more repeatedly washs with ethyl acetate and ether, must product d after drying;
Wherein product d is , described X is the one in Cl, Br, I, and q is the integer of 0 to 5.
Optimally, it also comprises step (5), and described step (5) is: by soluble in water for product d, add LiY and carry out ion-exchange, stirring reaction 5 ~ 10 is little of generation precipitation, collected by filtration, repeatedly wash with deionized water, dry that product e, described Y are BF 4, TFSI, PF 6in one.
Optimally, in described step (1), with mol ratio be 1:1 ~ 1.5.
Optimally, in described step (2), be 1:2 ~ 3 with the mol ratio of imidazoles.
Optimally, in described step (3), the mol ratio of product a and product b is 1:1 ~ 3.
Optimally, in described step (4), product c with mol ratio be 1:1 ~ 2.
Because technique scheme is used, the present invention compared with prior art has following advantages: the present invention has synthesized a kind of two imidazole type ionic crystals newly, on the one hand by introducing crystal primitive in its chemical structure, its scattering of light effect can be increased, in its chemical structure, introduce two imidazole group on the other hand, its specific conductivity (~ 10 can be improved -5s/cm), and the method preparing this pair of imidazole type ionic crystal is simple to operate, is conducive to commercially producing, has a extensive future.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of the two imidazole type ionic crystal of the present invention;
Fig. 2 is the nuclear magnetic spectrogram of two imidazole type ionic crystals of preparation in embodiment 1.
Embodiment
Embodiment 1
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, add 20mL acetone, 15mmol bis-butyl iodide, 10mmol successively , 20mmol K 2cO 3, 60 DEG C, under protection of inert gas, react and filter to get filtrate after 15 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization ;
(2) in another reaction vessel, add 20mL acetonitrile, 10mmol bis-butyl iodide, 25mmol imidazoles, 35mmol KOH successively, at room temperature react after 10 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization ;
(3) by 10mmol be added drop-wise to 30mmol acetone (20mL) solution in, at 30 DEG C, condensing reflux reacts 10 hours, rotary evaporation removing acetone, uses ethyl acetate and washed with diethylether three times respectively, after drying ;
(4) by 10mmol be dissolved in 20ml acetonitrile, add 12mmol methyl iodide, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation removing acetonitrile, then use ethyl acetate and washed with diethylether three times, after drying .
Embodiment 2
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, add 20mL acetone, 15mmol bis-butyl iodide, 10mmol successively , 20mmol K 2cO 3, 80 DEG C, under protection of inert gas, react and filter to get filtrate after 20 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization ;
(2) in another reaction vessel, add 20mL acetonitrile, 10mmol bis-butyl iodide, 25mmol imidazoles, 35mmol KOH successively, at room temperature react after 15 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization ;
(3) by 10mmol be added drop-wise to 30mmol acetone (20mL) solution in, at 30 DEG C, condensing reflux reacts 10 hours, rotary evaporation removing acetone, uses ethyl acetate and washed with diethylether three times respectively, after drying ;
(4) by 10mmol be dissolved in 20ml acetonitrile, add 12mmol butyl iodide, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation removing acetonitrile, then use ethyl acetate and washed with diethylether three times, after drying .
Embodiment 3
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, add 20mL acetone, 15mmol bis-butyl iodide, 10mmol successively , 20mmol K 2cO 3, 80 DEG C, under protection of inert gas, react and filter to get filtrate after 20 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization ;
(2) in another reaction vessel, add 20mL acetonitrile, 10mmol bis-butyl iodide, 25mmol imidazoles, 35mmol KOH successively, at room temperature react after 15 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization ;
(3) by 10mmol be added drop-wise to 30mmol acetone (20mL) solution in, at 30 DEG C, condensing reflux reacts 10 hours, rotary evaporation removing acetone, uses ethyl acetate and washed with diethylether three times respectively, after drying ;
(4) by 10mmol be dissolved in 20ml acetonitrile, add 12mmol iodohexane, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation removing acetonitrile, then use ethyl acetate and washed with diethylether three times, after drying .
Embodiment 4
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, 20mL acetone, 15mmol dibromobutane, 10mmol is added successively , 20mmol K 2cO 3, 80 DEG C, under protection of inert gas, react and filter to get filtrate after 20 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization ;
(2) in another reaction vessel, add 20mL acetonitrile, 10mmol dibromobutane, 25mmol imidazoles, 35mmol KOH successively, at room temperature react after 15 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization ;
(3) by 10mmol be added drop-wise to 30mmol acetone (20mL) solution in, at 30 DEG C, condensing reflux reacts 10 hours, rotary evaporation removing acetone, uses ethyl acetate and washed with diethylether three times respectively, after drying ;
(4) by 10mmol be dissolved in 20ml acetonitrile, add 12mmol n-butyl bromide, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation removing acetonitrile, then use ethyl acetate and washed with diethylether three times, after drying .
Embodiment 5
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, 20mL acetone, 15mmol dibromobutane, 10mmol is added successively , 20mmol K 2cO 3, 80 DEG C, under protection of inert gas, react and filter to get filtrate after 20 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization ;
(2) in another reaction vessel, add 20mL acetonitrile, 10mmol dibromobutane, 25mmol imidazoles, 35mmol KOH successively, at room temperature react after 15 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization ;
(3) by 10mmol be added drop-wise to 30mmol acetone (20mL) solution in, at 30 DEG C, condensing reflux reacts 10 hours, rotary evaporation removing acetone, uses ethyl acetate and washed with diethylether three times respectively, after drying ;
(4) by 10mmol be dissolved in 20ml acetonitrile, add 12mmol n-butyl bromide, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation removing acetonitrile, then use ethyl acetate and washed with diethylether three times, after drying ;
(5) by 10mmol be dissolved in 10mL water, add 12mmol LiBF 4carry out ion-exchange, stirring reaction 5 is little of generation precipitation, collected by filtration, with deionized water wash three times, dry
Embodiment 6
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
To get in 10mmol embodiment 4 preparation be dissolved in 10mL water, add the two fluoroform sulfimide lithium (LiTFSI) of 12mmol and carry out ion-exchange, stirring reaction 10 is little of generation precipitation, collected by filtration, with deionized water wash three times, dry .
Test example 1
The two imidazole type ionic crystal prepared by embodiment 1-6 and comparative example ionic crystal carry out specific conductivity test, concrete steps are as follows: described ionic crystal is placed in tabletting machine, the thin slice of 1cm*1cm is pressed under 10 ~ 20MPa, these thin slices are clipped in respectively between two pieces of stainless steel electrodes, the contact area of thin slice and stainless steel electrode is made to be 1cm*1cm, be connected on electrochemical workstation with two-probe method and test, the results are shown in Table shown in 1, wherein the chemical structural formula of comparative example ionic crystal is respectively ,
Two imidazole type ionic crystal specific conductivity test results prepared by table 1 embodiment 1-6
As can be seen from Table 1 in the present invention two imidazole type ionic crystal the equal comparative example of specific conductivity in the high order of magnitude of specific conductivity of single imidazole type ionic crystal, be more suitable for the ionogen preparing energy device, the performance of corresponding energy device can be improved.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (4)

1. a preparation method for two imidazole type ionic crystal, is characterized in that: it comprises the following steps:
(1) add successively in reaction vessel acetone, , , K 2cO 3, 60 ~ 80 DEG C, under protection of inert gas, react and filter to get filtrate after 10 ~ 15 hours, filtrate obtains product a through rotary evaporation, sherwood oil recrystallization; Described with mol ratio be 1:1 ~ 1.5;
(2) add successively in another reaction vessel acetonitrile, , imidazoles, KOH, filter to get filtrate after at room temperature reacting 10 ~ 20 hours, filtrate obtains product b through rotary evaporation, deionized water recrystallization;
(3) be added drop-wise to by product a in the acetone soln of product b, condensing reflux reaction 10 ~ 15 hours at 30 ~ 50 DEG C, rotary evaporation removing acetone, repeatedly washs with ethyl acetate and ether respectively, obtains product c after drying;
(4) product c is dissolved in acetonitrile, adds , KOH, filter to get filtrate after at room temperature reacting 10 ~ 20 hours, rotary evaporation removing acetonitrile, more repeatedly washs with ethyl acetate and ether, must product d after drying;
Wherein product d is , described X is the one in Cl, Br, I, and q is the integer of 0 to 5;
(5) by soluble in water for product d, add LiY and carry out ion-exchange, stirring reaction 5 ~ 10 is little of generation precipitation, collected by filtration, repeatedly wash with deionized water, dry product e, described Y are the one in BF4, two fluoroform sulfimide root, PF6.
2. the preparation method of according to claim 1 pair of imidazole type ionic crystal, is characterized in that: in described step (2), be 1:2 ~ 3 with the mol ratio of imidazoles.
3. the preparation method of according to claim 1 pair of imidazole type ionic crystal, is characterized in that: in described step (3), and product (a) is 1:1 ~ 3 with the mol ratio of product (b).
4. the preparation method of according to claim 1 pair of imidazole type ionic crystal, is characterized in that: in described step (4), product (c) with mol ratio be 1:1 ~ 2.
CN201310319862.6A 2013-07-26 2013-07-26 A kind of two imidazole type ionic crystal and preparation method thereof Expired - Fee Related CN103408496B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2481202A1 (en) * 2002-04-05 2003-10-23 University Of South Alabama Functionalized ionic liquids, and methods of use thereof
CN102568834A (en) * 2011-11-14 2012-07-11 江苏德威新材料股份有限公司 Electrolyte used for dye-sensitized solar cell and preparation method thereof
CN102592832A (en) * 2012-03-15 2012-07-18 苏州大学 Solid electrolyte for solar cell based on ionic crystal

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008005906A2 (en) * 2006-07-03 2008-01-10 Matheson Tri-Gas, Inc. Fluid storage and purification method and system using ionic liquid in particular di-imidazolium cation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2481202A1 (en) * 2002-04-05 2003-10-23 University Of South Alabama Functionalized ionic liquids, and methods of use thereof
CN102568834A (en) * 2011-11-14 2012-07-11 江苏德威新材料股份有限公司 Electrolyte used for dye-sensitized solar cell and preparation method thereof
CN102592832A (en) * 2012-03-15 2012-07-18 苏州大学 Solid electrolyte for solar cell based on ionic crystal

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Bis-imidazolium based poly(ionic liquid) electrolytes for quasi-solid-state dye-sensitized solar cells;Xiaojian Chen等;《J. Mater. Chem.》;20120713;第22卷;18018–18024 *

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