WO2014153642A1 - Synthesis of protic ionic liquids - Google Patents
Synthesis of protic ionic liquids Download PDFInfo
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- WO2014153642A1 WO2014153642A1 PCT/CA2014/000285 CA2014000285W WO2014153642A1 WO 2014153642 A1 WO2014153642 A1 WO 2014153642A1 CA 2014000285 W CA2014000285 W CA 2014000285W WO 2014153642 A1 WO2014153642 A1 WO 2014153642A1
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- Prior art keywords
- ionic liquids
- impr
- protic ionic
- protic
- acid
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 62
- 230000015572 biosynthetic process Effects 0.000 title description 12
- 238000003786 synthesis reaction Methods 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 23
- -1 carboxylate anions Chemical class 0.000 claims abstract description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims abstract description 7
- 150000007944 thiolates Chemical class 0.000 claims abstract description 5
- UTCSSFWDNNEEBH-UHFFFAOYSA-N imidazo[1,2-a]pyridine Chemical compound C1=CC=CC2=NC=CN21 UTCSSFWDNNEEBH-UHFFFAOYSA-N 0.000 claims description 47
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 150000001266 acyl halides Chemical class 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 claims 1
- 238000002411 thermogravimetry Methods 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- 238000000113 differential scanning calorimetry Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 5
- 230000009477 glass transition Effects 0.000 abstract description 4
- 238000004566 IR spectroscopy Methods 0.000 abstract description 3
- VNHBYKHXBCYPBJ-UHFFFAOYSA-N 5-ethynylimidazo[1,2-a]pyridine Chemical compound C#CC1=CC=CC2=NC=CN12 VNHBYKHXBCYPBJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 abstract description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract 1
- 238000004949 mass spectrometry Methods 0.000 abstract 1
- 235000015047 pilsener Nutrition 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- 239000003341 Bronsted base Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- AHRQMWOXLCFNAV-UHFFFAOYSA-O ethylammonium nitrate Chemical compound CC[NH3+].[O-][N+]([O-])=O AHRQMWOXLCFNAV-UHFFFAOYSA-O 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000005234 imidazo[1,2-a]pyridines Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012078 proton-conducting electrolyte Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/26—Thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/30—Ionic liquids and zwitter-ions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the present invention relates generally to novel protic ionic liquids with applications in CO2 capture, electrolytes for lithium ion and in general metal ion batteries and fuel cells where thermal stability and ionic conductivity are important.
- Ionic liquids can be divided to two broad categories, aprotic ionic liquids (AILs) and protic ionic liquids (PILs).
- AILs can be synthesized by several methods, e.g. transferring any group other than proton to basic site of the parent base molecule while protic ionic liquids are those which have been formed from proton transfer from a Bronsted acid to a Bronsted base.
- protic ionic liquids are those which have been formed from proton transfer from a Bronsted acid to a Bronsted base.
- AILs different properties and applications have been studied and reviewed widely in comparison with PILs. Nevertheless, the number of publications about synthesis and physicochemical properties of PILs as well of their applications has grown in recent years.
- PILs One of the most applicable features of PILs is their high proton conductivity even in anhydrous condition at elevated temperatures which makes them great candidate as proton conducting electrolyte in fuel cell applications.
- this type of PILs application largely depends on their degree of ionization which can be limited by incomplete proton transfer, aggregation or the formation of ion complexes.
- the ionic conductivity is also dependent on ion mobility and the number of charge carriers which rely on density, molecular weight and size of the ions.
- There are number of different techniques to provide information about ionicity of protic ionic liquids including NMR, changes in thermal properties as a function of stoichiometry, IR spectroscopy and using Walden plot.
- FIG. 1 shows Molecular structure of Thiolate ionic liquid
- Figure 4 shows Scheme 1 Formation of disulfide bond from thiolate group by molecular oxygen
- Figure 5 shows Structure of [ImPr][HS04]
- FIG. 7 shows Structure of [ImPr][Phth]
- FIG. 8 shows Structure of [ImPr][Ox]
- Figure 9 shows IR spectrums of the synthesized protic ionic liquids
- Figure 11 shows DSC spectrums of protic ionic liquids
- Figure 12 shows Arrhenius plot for [ImPr][Pim] protic ionic liquid
- Figure 13 shows Change of conductivity of ][ImPr] [Pirn] as function of temperature
- Figure 14 shows Walden plot from [ImPr] [pim] protic ionic liquid
- FIG. 15 shows Structure of [Imp][Maleamic]
- FIG. 16 shows Structure of [Imp][Trifluoroacetic]
- Figure 17 shows the amount of C0 2 absrobedby [Imp][Maleamic]
- the [ImPr] derivatives are such as but not limited to alkyl, aryl, halogens, halogenated alkyl and aryls, amines, amides, alkyl and aromatic alcoholic groups, nitroso, phenyl, organic boranes and diboranes, thiols, acylated groups, Benzoylated groups, Acyl halides, Anhydrides, Bisacylamides, esters, Silylated, Silanes, Silazanes, Si-OR where R could be H, halogens and any alkyl or aryl group, and mixtures of above.
- the inventors further claim a method to synthesize protic ionic liquids using imidazo [1 ,2 a] pyridine as a base wherein 1,2 benzenedithiol, oxalic acid, phthalic acid and pilmelic acid are applied as anion counterpart of protic ionic liquids and wherein any organic acid or acids can be applied as anion counterpart of protic ionic liquids.
- melting point of all synthesized ionic liquids is below 100 degrees centigrade categorizing them as room temperature ionic liquids.
- Imidazo [1,2 a] pyridine [ImPr]. is used as base in synthesis of protic ionic liquids.
- 1 ,2 benzenedithiol, oxalic acid, phthalic acid [Phth] and pilmelic acid [Pirn] were applied as anion counterpart of protic ionic liquids. This can be extended to all organic acids.
- the melting point of all synthesized ionic liquids were below lOOC categorizing them as room temperature ionic liquids.
- the ionic conductivity and viscosity measurements as the function of temperature are done for [ImPr]. [Pirn].
- This protic ionic liquid showed relatively better ionic conductivity in comparison with imidazolium-based protic ionic liquids.
- the first ionic liquid based on a bisulfide [IMpr] system ( Figure 3) is made.
- Imidazo [1,2 a] pyridine 98%, Pimelic acid 98%, Oxalic acid 99% and Phthalic acid 99% are purchased from Sigma Aldrich. Benzene 1,2 dithiol 97% is purchased from Alpha Aesar. All protic ionic liquids were synthesized solvent free. Preparation and characterization of each protic ionic liquid is described individually in following sections. Thermal stability and phase behavior of the samples are investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) respectively.
- TGA thermogravimetric analysis
- DSC differential scanning calorimetry
- Decomposition temperature of [ImPr][Pim] and [ImPr][Ox] is 175°C and 165°C respectively which decomposition temperature is defined as where there is 10% weight loss in TGA curve.
- TGA spectrums of these two PILs show one step process. Two process TGA process has been observed for [ImPr][Phth], [ImPr][BDT] and [ImPr][HS0 4 ]. The initial step for [ImPr][HS0 4 ] and [ImPr][Phth] is related to water loss in the system.
- the decomposition temperatures of [ImPr][Phth] and [Impr][HS0 4 ] which have been determined from the second step of the process are 175 °C and 336°C respectively .
- TGA curve of the [ImPr][BDT] shows two step process which the first one should be related to the decomposition process of [ImPr][BDT] and the second process can be related to the decomposition process of oxidation product of [ImPr][BDT].
- the decomposition temperature of [ImPr][BDT] is estimated as 126°C.
- the phase transitions of the protic ionic liquids were studied using DSC Q200 V24.8 Build 120 at Dalhousie University. The samples heated up 400 °C and cooled down to -150°C on Aluminum Hermetic pan under nitrogen and Helium atmosphere. The heating and cooling rate was usually 10 °C/min. All protic ionic liquids show melting points below 100°C and glass transition temperature is observed for [ImPr][Pim], [ImPr][BDT] and [ImPr][Ox] at -47, 5 and 7 °C . The DSC spectrums of the ionic liquids are shown in Figure 11.
- the Waldon plot is applied for [ImPr] [Pirn] protic ionic liquids ( Figure 14) by calculating the equivalent conductivity at different temperatures by considering the density (1.2 g/cm 3 ) and molecular weight (278.3 g/mol) values.
- [ImPr] [Pirn] shows similar behavior to the most protic ionic liquid by deviation from Walden plot which is indicative of incomplete proton transfer.
- PIL [Imp][Maleamic] Figure 15 absorbs C02 as demonstrated by Figure 17 and PIL [Imp][Trifluoroacetic] Figure 16 absorbs C02 as demonstrated by Figure 18. Since the IR spectra after C02 is absorbed suggests transformation of C02 to a new value added chemical followed by a chemical reaction with C02/ PIL. The reaction is due to polarizing C02 upon absorption on PIL and therefore changing the geometry of C02 and weakening its CO bonds.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
Novel imidazolium [1,2a] pyridine (ImPr) based protic ionic liquids with thiolate/disulfide and different carboxylate anions have been synthesized and characterized by NMR, IR and Mass spectroscopy. Thermogravimetry analysis (TGA) has been done to investigate the thermal behavior of these protic ionic liquids. Their decomposition temperatures are determined in the range of 126-175°C except [ImPr][HSO4] which is most stable with decomposition temperature of 326°C. Differential Scanning Calorimetry (DSC) has been used to analyze phase behavior of these protic Ionic liquid. Glass transition temperature has been observed for all the synthesized PILs. Ionic conductivity of [Impr] [Pim] is measured at 25 °C, 58.6 µS/cm, which is a relatively good conductivity in comparison with imidazolium-based ionic liquids. All ionic liquids were synthesized using an environmentally friendly solvent free method.
Description
Synthesis of Protic Ionic Liquids
FIELD OF THE INVENTION
The present invention relates generally to novel protic ionic liquids with applications in CO2 capture, electrolytes for lithium ion and in general metal ion batteries and fuel cells where thermal stability and ionic conductivity are important.
BACKGROUND OF THE INVENTION
Ionic liquids (Figure 1) have been considered as greener alternatives to conventional solvents. They provide a new approach to sustainable chemistry due to their stability, non-inflammability, negligible vapour pressure, tunable properties and catalytic behaviour make them great solvents or catalysts in many organic syntheses
Ionic liquids can be divided to two broad categories, aprotic ionic liquids (AILs) and protic ionic liquids (PILs). AILs can be synthesized by several methods, e.g. transferring any group other than proton to basic site of the parent base molecule while protic ionic liquids are those which have been formed from proton transfer from a Bronsted acid to a Bronsted base. AILs different properties and applications have been studied and reviewed widely in comparison with PILs. Nevertheless, the number of publications about synthesis and physicochemical properties of PILs as well of their applications has grown in recent years. One of the most applicable features of PILs is their high proton conductivity even in anhydrous condition at elevated temperatures which makes them great candidate as proton conducting electrolyte in fuel cell applications. However this type of PILs application largely depends on their degree of ionization which can be limited by incomplete proton transfer, aggregation or the formation of ion complexes. The ionic conductivity is also dependent on ion mobility and the number of charge carriers which rely on density, molecular weight and size of the ions. There are number of different techniques to provide information about ionicity of protic ionic liquids including NMR, changes in thermal
properties as a function of stoichiometry, IR spectroscopy and using Walden plot. Among these techniques Walden plot which is based on classic Walden rule is a convenient method to assess ionicity of protic ionic liquids. The Walden rule relates the ionic mobility represented by equivalent conductivity (Λ) to the fluidity (η"') of the medium. In the ideal case, when the ion- ion interaction is negligible, the slope of the plot should be unity. Highly diluted aqueous KC1 solution is used to establish the position of ideal case.
Along with PILs applications in biological systems and chromatography they can be used as media and catalyst in numerous numbers of organic reactions. PILs can also act as hyperpolar media because of their high dielectric conductivities caused by extended hydrogen bonding. The polarity of ILs decrease with the increase in distance between ions due to decrease in effective charge density between them. This type of protic ionic liquids are capable of promoting the self- assembly of amphiphiles by formation of hydrogen bonded network. The best know example of this group of PILs is ethylammonium nitrate (EAN) which has many similarities to water including high polarity. It has been identified that thermal stability and physicochemical properties of protic ionic liquids including their ionic conductivity and polarity firmly depend on nature of the anion and cation as well as length of alkyl chain, alkyl branching and the number of hydroxyl groups involving in their structure. Protic ionic liquids structure-properties correlation and their tunable behavior of some of the ammonium, imidazolium and heterocyclic amine have been investigated and compared.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows Molecular structure of Thiolate ionic liquid
Figure 2 shows ORTEP drawing of the product structure gained from x-ray crystallography Figure 3 shows Structure of the bisulfide ionic liquid
Figure 4 shows Scheme 1 Formation of disulfide bond from thiolate group by molecular oxygen Figure 5 shows Structure of [ImPr][HS04]
Figure 6 shows Structure of [ImPr][Pim]
Figure 7 shows Structure of [ImPr][Phth]
Figure 8 shows Structure of [ImPr][Ox]
Figure 9 shows IR spectrums of the synthesized protic ionic liquids
Figure 10 shows Thermogravimetry of protic ionic liquids
Figure 11 shows DSC spectrums of protic ionic liquids
Figure 12 shows Arrhenius plot for [ImPr][Pim] protic ionic liquid
Figure 13 shows Change of conductivity of ][ImPr] [Pirn] as function of temperature
Figure 14 shows Walden plot from [ImPr] [pim] protic ionic liquid
Figure 15 shows Structure of [Imp][Maleamic]
Figure 16 shows Structure of [Imp][Trifluoroacetic]
Figure 17 shows the amount of C02 absrobedby [Imp][Maleamic]
Figure 18 shows the amount of C02 absrobedby [Imp][Trifluoroacetic]
DETAILS OF THE SPECIFICATION
The inventors claim novel protic ionic liquids based on [ImPr] as base and all its derivatives and following acids [HS04], [Pirn] (and all [Pirn derivatives]), [thiolates], [bisulfides], [Phth] and all [Phth derivatives], [Oxalic acid [Ox] and all Ox derivatives], [Maleamic and all its derivatives], [Trifluoroacetic and polyfluoro organic acids]. The [ImPr] derivatives are such as but not limited to alkyl, aryl, halogens, halogenated alkyl and aryls, amines, amides, alkyl and aromatic alcoholic groups, nitroso, phenyl, organic boranes and diboranes, thiols, acylated groups, Benzoylated groups, Acyl halides, Anhydrides, Bisacylamides, esters, Silylated, Silanes, Silazanes, Si-OR where R could be H, halogens and any alkyl or aryl group, and mixtures of above.
The inventors further claim a method to synthesize protic ionic liquids using imidazo [1 ,2 a] pyridine as a base wherein 1,2 benzenedithiol, oxalic acid, phthalic acid and pilmelic acid are applied as anion counterpart of protic ionic liquids and wherein any organic acid or acids can be applied as anion counterpart of protic ionic liquids. In this method melting point of all synthesized ionic liquids is below 100 degrees centigrade categorizing them as room temperature ionic liquids.
Imidazo [1,2 a] pyridine [ImPr]. is used as base in synthesis of protic ionic liquids. 1 ,2 benzenedithiol, oxalic acid, phthalic acid [Phth] and pilmelic acid [Pirn] were applied as anion counterpart of protic ionic liquids. This can be extended to all organic acids. The melting point of all synthesized ionic liquids were below lOOC categorizing them as room temperature ionic liquids. The ionic conductivity and viscosity measurements as the function of temperature are done for [ImPr]. [Pirn]. This protic ionic liquid showed relatively better ionic conductivity in comparison with imidazolium-based protic ionic liquids. The first ionic liquid based on a bisulfide [IMpr] system (Figure 3) is made.
Experimental Details
Imidazo [1,2 a] pyridine 98%, Pimelic acid 98%, Oxalic acid 99% and Phthalic acid 99% are purchased from Sigma Aldrich. Benzene 1,2 dithiol 97% is purchased from Alpha Aesar. All protic ionic liquids were synthesized solvent free. Preparation and characterization of each protic ionic liquid is described individually in following sections. Thermal stability and phase behavior of the samples are investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) respectively.
Differential scanning calorimetry (DSC) was performed with Q200 DSC from TA instrument under helium atmosphere, and thermal gravimetric analysis (TGA) was conducted with a Mettler Toledo 851 system under a nitrogen atmosphere. An indium standard was used to calibrate the DSC temperature (0.3 °C) and enthalpy scale. The samples were run in an aluminum pan in a sealed furnace, and were cooled to -150 °C before heating at rates of 10 deg/ min.
HNMR (JEOL-270MHz) has been done in CDCb (>98% Sigma Aldrich). By comparing the product spectrum to the starting material there is no sign of any side reaction but there is a downfield shift for BDT peaks and upfield shift for imidazolium [1,2 a] pyridine (ImPr).
Raman spectroscopy has been used as one of the useful and convenient tools for characterization of compounds at solid state. Each of white and solid powders placed between two thin glass slides and sealed under nitrogen. Raman is done at room temperature via 64 scans for starting material, yellow powder and the white one. Complete ionization for the white product was evidenced from absence of SH group at 2420 cm"1. SH peak at 2420 cm"1 for the yellow product is representative of partial ionization. The N-H+ in the product appeared at 3030 cm"1 for both white and yellow product. The white product re-crystallized in toluene by slow evaporation in glove- box. Two crystals, one yellow and one red were obtained after 3 weeks
Crystallography x ray diffraction of the red crystal confirms formation of disulfide bond in the system resulting from oxidation of thiol group by molecular oxygen in the air (Figure 4). Also as it is illustrated in the ORTEP drawing (Figure 2), only one of the thiol groups is depronotated and the proton transferred to the nitrogen of [1,2 a] imidazo pyridine.
Synthesis and characterization of [ImPr] [HSO4] (Figure 5)
0.05 mL H2S04 (95%) was added to 0.1 mL Imidazo [1,2 a] pyridine dropwise while the container is kept in pre-cooled (5-8 °C) ultrasonic bath (Brasonic-50/60 Htz). Then the reaction mixture stirred well for 2 minutes and transferred again to ultrasonic bath 15 minutes. A purple solid sample formed which washed by diethyl ether to remove non-ionic compounds from that. The solid was pumped overnight while it is heated at 40 °C oil bath.
Synthesis and characterization of [ImPr] [Pim] (Figure 6)
0.32 g pimelic acid was added to O.lmL Imidazo [1,2 a] pyridine and heated up to 80 °C for one hour under constant stirring. A green viscose liquid has been formed which was washed by diethyl ether two times to remove non-ionic remaining from the sample.
Synthesis and characterization of [ImPr] [Phth] (Figure 7)
0.32 g phthalic acid was added to O. lmL Imidazo [1,2 a] pyridine and heated up to 80 °C for one hour under constant stirring. A white/yellowish solid has been obtained which was washed by diethyl ether two times to remove non-ionic remaining from the sample.
Synthesis and characterization of [ImPr] [Ox] (Figure 8)
0.18 g oxalic acid was added to O.lmL Imidazo [1,2 a] pyridine and heated up to 80 °C for one hour under constant stirring. A white/yellowish solid has been obtained which was washed by diethyl ether two times to remove non-ionic remaining from the sample.
IR spectroscopy of synthesized PILs
IR spectrum of the products was conducted in dilute solution of the CHC13 via KCl disk. IR spectrums (Figure 9) show NH peaks in the range of 3000-3200 cm"1 which confirms proton transfer from the bronsted acid to bronsted base.
Thermal stability
Thermal stability of the synthesized ionic liquids was investigated by thermogravimetry analysis Figure 10 by using NETZSCH- TG- 209F3 themogravimetry analyzer at Dalhousie University. Sample weighted and placed in A1203 crucible and heated up to 475°C with the heating rate of 10 °C/min. The degradation has been completed in Argon atmosphere.
Decomposition temperature of [ImPr][Pim] and [ImPr][Ox] is 175°C and 165°C respectively which decomposition temperature is defined as where there is 10% weight loss in TGA curve. TGA spectrums of these two PILs show one step process. Two process TGA process has been observed for [ImPr][Phth], [ImPr][BDT] and [ImPr][HS04]. The initial step for [ImPr][HS04] and [ImPr][Phth] is related to water loss in the system. The decomposition temperatures of [ImPr][Phth] and [Impr][HS04] which have been determined from the second step of the process are 175 °C and 336°C respectively . TGA curve of the [ImPr][BDT] shows two step process which the first one should be related to the decomposition process of [ImPr][BDT] and the second process can be related to the decomposition process of oxidation product of [ImPr][BDT]. The decomposition temperature of [ImPr][BDT] is estimated as 126°C.
DSC Analysis
The phase transitions of the protic ionic liquids were studied using DSC Q200 V24.8 Build 120 at Dalhousie University. The samples heated up 400 °C and cooled down to -150°C on Aluminum Hermetic pan under nitrogen and Helium atmosphere. The heating and cooling rate was usually 10 °C/min. All protic ionic liquids show melting points below 100°C and glass transition temperature is observed for [ImPr][Pim], [ImPr][BDT] and [ImPr][Ox] at -47, 5 and 7 °C . The DSC spectrums of the ionic liquids are shown in Figure 11.
Tm(°C) Tg (°C) Ts-Lc fC) Td (°C)
[lm Pr] [BDT] 71 5 60 126
[lmPr] [Pim] n.d -47 n.d 175
[lmpr] [Ox] 99 7 n.d 165
[lmPr] [phth] 84 6 48 175
Table 1 Melting point (Tm), glass transition temperature(Tg), solid-solid transition (TS-LC) and decomposition temperature (Td) of protic ionic liquids
Viscosity measurement
The viscosity of [ImPr][Pim] ionic liquid which is liquid at room temperature was measured using BookField-LV viscometer at different temperatures and the Arrhenius plot is illustrated based on its glass transition temperature at -47°C (Figure 12). The Arrhenius behavior is represented by the solid line based on Vogel-Fulcher-Tamman equation (equation 1 ) where D is proportional to fragility. Deviation from the line to the right bottom of the plot shows the fragile behavior. The term of fragility is attributed to the compounds which by increasing the temperature, their viscosity will decrease at a faster rate than predicted by the Arrhenius relationship. Most of the protic ionic liquids show intermediate to high fragility as has been investigated by Angel et al.
Table 2 change in viscosity of [lmPr] [Pimelic] as function of temperature
Ionic Conductivity measurement
The ionic conductivity of [Pimelic acid][ImPr] was measured at different temperatures using SUNTEX Conductivity Meter- SCI 70 with cell constant of 1cm"1. The conductivity versus temperature is plotted in Figure 13. Conductivity of [Pimelic acid][ImPr] at 25°C is 58.6 μ8/ΰΐ which is relatively good conductivity in comparison with imidazolium based protic ionic liquids but this value is lower than the conductivity of most of the pyridinium protic ionic liquids.
The Waldon plot is applied for [ImPr] [Pirn] protic ionic liquids (Figure 14) by calculating the equivalent conductivity at different temperatures by considering the density (1.2 g/cm3) and molecular weight (278.3 g/mol) values. [ImPr] [Pirn] shows similar behavior to the most protic ionic liquid by deviation from Walden plot which is indicative of incomplete proton transfer.
Table 1 log of equivalent conductivity and log of fluidity in the range of temperature of 15C to 50 C
Crystalline structure
SEM was carried out on the surface of the [ImPr][Phth], [ImPr] [Ox] and [ImPr][HS04] prepared by melting the powder and subsequent solidification. The crystalline structure was observed for all these three samples.
Applications
Some important applications: Designer solvents, catalysts, electrolytes in fuel cells, nanotechnology, electrolytes in batteries, medium for chemical transformation of biomass waste and C02 to value added material (by chemical reaction following C02 absorption).
The PIL [Imp][Maleamic] Figure 15 absorbs C02 as demonstrated by Figure 17 and PIL [Imp][Trifluoroacetic] Figure 16 absorbs C02 as demonstrated by Figure 18. Since the IR spectra after C02 is absorbed suggests transformation of C02 to a new value added chemical followed by a chemical reaction with C02/ PIL. The reaction is due to polarizing C02 upon absorption on PIL and therefore changing the geometry of C02 and weakening its CO bonds.
Claims
1. A method to synthesize protic ionic liquids using imidazo [1 ,2 a] pyridine as a base.
2. The method of Claim 1, wherein 1 ,2 benzenedithiol, oxalic acid, phthalic acid and pilmelic acid are applied as anion counterpart of protic ionic liquids.
3. The method of Claim 1, wherein any organic acid or acids can be applied as anion counterpart of protic ionic liquids.
4. The method of Claim 1 wherein melting point of all synthesized ionic liquids is below 100 degrees centigrade categorizing them as room temperature ionic liquids.
5. The method of Claim 1 wherein the protic ionic liquid has relatively better ionic conductivity in comparison with imidazolium-based protic ionic liquids.
6. A method to produce protic ionic liquids based on a bisulfide [IMpr] system
7. A method to generate value added C02 by interacting CCtewith Protic ionic liquid synthesized in claim 1.
8. A protic ionic liquid based on [ImPr] or any of its derivatives as a base and an acid.
9. The derivatives of claim 8 comprising at least any one of alkyl, aryl, halogens, halogenated alkyl and aryls, amines, amides, alkyl and aromatic alcoholic groups, nitroso, phenyl, organic boranes and diboranes, thiols, acylated groups, Benzoylated groups, Acyl halides, Anhydrides, Bisacylamides, esters, Silylated, Silanes, Silazanes, Si-OR where R could be H, halogens and any alkyl or aryl group or mixtures of above.
10. The acid in claim 8 comprised any one of [HS04], [Pirn] or any [Pirn derivatives], [thiolates], [bisulfides], [Phth] or any [Phth derivatives], [Oxalic acid [Ox] or any Ox derivatives], [Maleamic acid or any of its derivatives] or [Trifluoroacetic and polyfluoro organic acids].
1 1. A method to generate value added CO2 by interacting C02with Protic ionic liquid of claim 8.
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| CN107398146A (en) * | 2017-08-16 | 2017-11-28 | 天津大学 | A kind of protonized ionic liquid absorbent containing metal salt and its application |
| US9859531B2 (en) | 2015-02-06 | 2018-01-02 | Ovonic Battery Company, Inc. | Alkaline and non-aqueous proton-conducting pouch-cell batteries |
| CN110398514A (en) * | 2018-04-24 | 2019-11-01 | 恒天纤维集团有限公司 | A kind of method of metals content impurity in quick judgement cellulose glue |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9859531B2 (en) | 2015-02-06 | 2018-01-02 | Ovonic Battery Company, Inc. | Alkaline and non-aqueous proton-conducting pouch-cell batteries |
| US10476044B2 (en) | 2015-02-06 | 2019-11-12 | Ovonic Battery Company, Inc. | Alkaline and non-aqueous proton-conducting pouch-cell batteries |
| CN107398146A (en) * | 2017-08-16 | 2017-11-28 | 天津大学 | A kind of protonized ionic liquid absorbent containing metal salt and its application |
| CN110398514A (en) * | 2018-04-24 | 2019-11-01 | 恒天纤维集团有限公司 | A kind of method of metals content impurity in quick judgement cellulose glue |
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