• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Bisimidazolium salts for energy storage. The present invention relates to the use of compounds of formula (I) in the storage of thermal energy, with energy storage devices comprising said compounds of formula (I), as well as with compounds of formula (II) and their process of obtaining. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2611780A1
    申请号:ES201531615
    申请日:2015-11-10
    公开日:2017-05-10
    发明作者:Ramón CANELA GARAYOA；Mercè BALCELLS FLUVIÀ；Jordi Eras Joli；Nuria SALA MARTÍ；Edinson YARA VARON；Marc ESCRIBÀ GELONCH；Camila BARRENECHE GÜERISOLI；Ingrid MARTORELL BOADA；Luisa Fernanda CABEZA FABRA
    申请人:Universitat de Lleida；
    IPC主号:
    专利说明:

    image 1
    image2
    image3
    image4
    image5
    image6
    In the context of the present invention, "alkyl" refers to a linear or branched hydrocarbon chain radical consisting of carbon and hydrogen atoms, which does not contain unsaturations, having the number of carbon atoms indicated, for example 1 at 20 carbon atoms, from 10 to 20 carbon atoms, from 1 to 12 carbon atoms, from 1 to 6 carbon atoms, from 3 to 6 carbon atoms, and which is attached to the rest of the molecule through a bond simple. Examples of alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n- nonyl, n-decanyl, n-undecanyl, n-dodecanyl, n-tridecanyl, n-tetradecanyl, npentadecanyl, etc.
    Here, "alkenyl" refers to a linear or branched hydrocarbon chain radical consisting of carbon and hydrogen atoms, containing at least one unsaturation, having the number of carbon atoms indicated, for example from 2 to 20 carbon atoms, from 3 to 20 carbon atoms, from 2 to 6 carbon atoms, from 3 to 6 carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of alkenyl are vinyl, n-propenyl, i-propenyl, n-butenyl, n-pentenyl, etc.
    Here, "aryl" refers to an aromatic hydrocarbon radical consisting of carbon and hydrogen atoms, which has the number of carbon atoms indicated, such as 6 to 10 carbon atoms, and which is attached to the rest of the molecule through a simple bond. Examples of aryl are phenyl and naphthyl.
    Examples of C1 alkyl substituted with one, two or three C6-C10 aryl groups are phenylmethyl, diphenylmethyl and trinaphthylmethyl, among others. Said C6-C10 aryl substituents may be the same.
    or different.
    Here, "monovalent anion" refers to an inorganic or organic anion with a single negative charge that can form an ionic bond with a cation of an imidazolium derivative. Examples of monovalent anions are PF6-, Cl-, Br-, I-, F-, BF4-, NO3, NO2-, SCN-, BrO3-, IO3-, HCO3-, HCOO-, CH3COO-, HSO4-, HSO3 -and H2PO3-.
    In this document, "divalent anion" refers to an inorganic or organic anion with two negative charges that can form an ionic bond with two cations of an imidazolium derivative. Examples of divalent anions are oxalate (COO) 22-, malonate -OOCCH2COO-, tartrate -OOC-CHOH-CHOH-COO-, CO32-, SO42-, SO32- and HPO32-.
    In a preferred embodiment of the use of the compounds of formula (I), R1 and R2 are the same.
    In an alternative embodiment, R1 and R2 are different.
    In another preferred embodiment of the use of the compounds of formula (I), R1 and R2 are independently a C1-C12 straight or branched alkyl, preferably C1-C6 straight or branched alkyl, preferably R1 and R2 are independently selected from the group consisting of butyl, isopropyl, propyl, ethyl and methyl, more preferably both are the same, even more preferably both are butyl.
    In another preferred embodiment of the use of the compounds of formula (I), R3 is H. In another embodiment, R3 is R4CO.
    In another embodiment of the use of the compounds of formula (I), R3 is R4CO and R4 is selected from the group consisting of C10-C20 linear alkyl, C3-C6 branched alkyl, methyl (i.e. C1 alkyl) substituted with one, two or three C6-C10 aryl, C2-C6 linear alkenyl, naphthyl and phenyl groups, preferably from the group consisting of tert-butyl, isobutyl, isopropyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, pentadecanyl, vinyl, ethenyl, 1 -propenyl, diphenylmethyl, phenylmethyl, naphthyl and phenyl, more preferably from the group consisting of tert-butyl, pentadecanyl, vinyl and naphthyl.
    In another embodiment of the use of the compounds of formula (I), R3 is R4CO and R4 is selected from the group consisting of C10-C20 linear alkyl, C3-C6 branched alkyl, C2-C6 linear alkenyl, naphthyl and phenyl, preferably of the group consisting of tert-butyl, isobutyl, isopropyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, pentadecanyl, vinyl, ethenyl, 1-propenyl, naphthyl and phenyl, more preferably from the group consisting of tert-butyl, pentadecanyl , vinyl and naphthyl.
    In a preferred embodiment of the use of the compounds of formula (I), n is 2 and A is a monovalent anion. Preferably A is selected from the group consisting of PF6-, Cl-, Bry BF4-, more preferably from the group consisting of PF6- and Cl-, even more preferably A is Cl-. The selection of Cl-as monovalent anion A yields compounds with higher solidification and fusion enthalpies.
    In an alternative embodiment of the use of the compounds of formula (I), n is 1 and A represents a divalent anion.
    image7
    image8
    R1 and R2 are independently selected from the group consisting of linear or branched C1-C12 alkyl, wherein C1 alkyl is optionally substituted with one, two or three C6-C10 aryl groups; linear or branched C2-C12 alkenyl and C6-C10 aryl; R4 is selected from the group consisting of C1-C20 linear or branched alkyl, wherein C1 alkyl is optionally substituted with one, two or three C6-C10 aryl groups; linear or branched C3-C20 alkenyl and C6-C10 aryl; A is a monovalent or divalent anion; and n is 2 when A is a monovalent anion or n is 1 when A is a divalent anion.
    In a preferred embodiment of the compounds of formula (II), R1 and R2 are the same. In an alternative embodiment, R1 and R2 are different.
    In another preferred embodiment of the compounds of formula (II), R1 and R2 are independently a C1-C12 linear or branched alkyl, preferably R1 and R2 are independently a C1-C6 linear or branched alkyl, preferably R1 and R2 are independently selected from the group consisting of butyl, isopropyl, propyl, ethyl and methyl, more preferably both are the same, even more preferably both are butyl.
    In another embodiment of the compounds of formula (II), R4 is selected from the group consisting of C10-C20 linear alkyl, C3-C6 branched alkyl, methyl (i.e. C1 alkyl) substituted with one, two or three C6 aryl groups -C10, C3-C6 linear alkenyl, naphthyl and phenyl; preferably from the group consisting of tert-butyl, isobutyl, isopropyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1-propenyl, diphenylmethyl, phenylmethyl, pentadecanyl, naphthyl and phenyl, more preferably from the group consisting of tert-butyl , pentadecanyl and naphthyl.
    In another embodiment of the compounds of formula (II), R4 is selected from the group consisting of C10-C20 linear alkyl, C3-C6 branched alkyl, naphthyl and phenyl, preferably from the group consisting of tert-butyl, isobutyl, isopropyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, pentadecanyl, naphthyl and phenyl, more preferably from the group consisting of tert-butyl, pentadecanyl, vinyl and naphthyl.
    In one embodiment of the compounds of formula (II), n is 2 and A is a monovalent anion. Preferably A is selected from the group consisting of PF6-, Cl-, Br- and BF4-, more preferably from the group consisting of PF6- and Cl-, even more preferably A is Cl-. The selection of Cl-as monovalent anion A yields compounds with higher solidification and fusion enthalpies.
    In an alternative embodiment of the compounds of formula (II), n is 1 and A represents a divalent anion.
    In a particular embodiment of the compounds of formula (II), R1 and R2 are independently a C1-C6 linear or branched alkyl; R4 is selected from the group consisting of C10-C20 linear alkyl, C3-C6 branched alkyl, naphthyl and phenyl; n is 2 and A represents a monovalent anion selected from the group consisting of PF6- and Cl-, preferably Cl-.
    In another particular embodiment of the compounds of formula (II), R1 and R2 are independently selected from the group consisting of butyl, isopropyl, propyl, ethyl and methyl; R4 is selected from the group consisting of C10-C20 linear alkyl, C3-C6 branched alkyl, naphthyl and phenyl; n is 2 and A represents a monovalent anion selected from the group consisting of PF6- and Cl-, preferably Cl-.
    In another particular embodiment of the compounds of formula (II), R1 and R2 are butyl; R4 is selected from the group consisting of C10-C20 linear alkyl, C3-C6 branched alkyl, naphthyl and phenyl; n is 2 and A represents a monovalent anion selected from the group consisting of PF6- and Cl-, preferably Cl-.
    In another particular embodiment of the compounds of formula (II), R1 and R2 are butyl; R4 is selected from the group consisting of tert-butyl, pentadecanyl and naphthyl; n is 2 and A represents a monovalent anion selected from the group consisting of PF6- and Cl-, preferably Cl-.
    In another particular embodiment of the compounds of formula (II), R1 and R2 are butyl; R4 is selected from the group consisting of tert-butyl, pentadecanyl and naphthyl; n is 2 and A is Cl-.
    The present invention also relates to any combination of the particular and preferred embodiments described above.
    In another embodiment of the compounds of formula (II), said compound is selected from the group consisting of: 1,1'- (2- (2,2-dimethylpropanoyloxy) -1,3-propanediyl) bis (3 -butyl-1H-imidazolium),
    image9
    image10
    Chlorination agent is selected from the group consisting of chlorotrimethylsilane, CaCl2 in the presence of H3PO4 and AlCl3 (in particular in the form of hexahydrate, ie AlCl3 · 6H2O) optionally in the presence of H3PO4. More preferably the chlorination agent is chlorotrimethylsilane.
    Preferably, step a) is carried out by heating (for example by conventional or microwave heating) between 60 ° C and 250 ° C, preferably between 75 ° C and 95 ° C, more preferably at 80 ° C, preferably in the absence of solvent (especially when the Chlorination agent can act both as a reagent and solvent, as in the case of chlorotrimethylsilane). Suitable solvents for this stage are aliphatic and aromatic hydrocarbons, such as hexane, heptane, cyclohexane, benzene, toluene, xylene; eutectic solvents, such as mixtures of glycerol and choline chloride, glycerol and hydroxycoline, urea and choline chloride, thiourea and choline chloride; ethers, such as diethyl ether, dioxane, tetrahydrofuran and methyltetrahydofuran; and halogenated solvents such as dichloromethane, chloroform.
    The appropriate time to complete the reaction of step a) can be determined by the person skilled in the art by usual procedures such as thin layer chromatography (TLC), nuclear magnetic resonance imaging (NMR) or high performance liquid chromatography (HPLC). This time will depend on the heating system used. In particular, conventional heating is maintained at least 30 h, preferably at least 40 h, more preferably at least 48 h, even more preferably between 40 h and 50 h. Microwave heating is preferably maintained 5 min, more preferably 10 min, even more preferably between 15 min and 20 min.
    The compound of formula (IV) obtained in step a) can be purified using conventional techniques such as extraction, chromatography, crystallization or distillation.
    Step b) of the process is preferably carried out by heating between 80 ° C and 250 ° C, preferably between 100 ° C and 120 ° C, more preferably at 110 ° C, in the absence of solvent. The appropriate time to complete the reaction can be determined by the person skilled in the art by usual procedures such as thin layer chromatography (TLC), nuclear magnetic resonance imaging (NMR) or high performance liquid chromatography (HPLC). In a particular embodiment, the heating is maintained at least 30 h, preferably at least 40 h, more preferably at least 48 h, even more preferably between 40 h and 50 h. Preferably the reaction is carried out in an inert atmosphere,
    image11
    In the particular case where R3 is H in the compounds of formula (I) the procedure described in Straubinger et al. (J. Organomet. Chem., 2011, 696, 687-6929, which is incorporated by reference herein with respect to the synthesis procedures described), which comprises reacting 1,3-dibromopropan-2-ol with a compound of formula (V) or formula (VI) as described above depending on whether R1 and R2 are the same or different, in tetrahydrofuran, at 100 ° C and in a pressure tube, to provide a compound of formula (I), in where n is 2 and A represents Br-. The preparation of the compounds of formula (I) wherein n is 1 or 2, as defined above for the compounds of formula (I) and A represents a monovalent or divalent anion other than Br-, as defined above for the compounds of formula (I), it is carried out by an anion exchange reaction, such as by reaction of the bromide salt obtained with a salt of A as described in step c) of the process of obtaining the compounds of formula (II), preferably using water as solvent.
    The following non-limiting examples are intended to illustrate the present invention and should not be construed as limitations on the scope of the present invention.
    Examples Materials and methods
    Materials and reagents
    Acrylic, 1-naphthylcarboxylic, palmitic and pivotal acids were obtained from Sigma-Aldrich (Sigma-Aldrich Química, S.A., Madrid, Spain). Hexane, methanol, ethanol, acetone, acetonitrile, diethyl ether, isopropanol and dichloromethane were obtained from T.J. Baker (Quimega, Lleida, Spain). 1,3-Dichloro-2-propanol, N, N-dicyclohexylcarbondiimide (DCC) and potassium hexafluorophosphate (KPF6) were obtained from Across Organics (Barcelona, Spain). Potassium hydroxide was purchased from Panreac (Barcelona, Spain).
    Crude glycerol was obtained from an industrial biodiesel supplier that used an alkali catalyzed alcoholysis procedure (Raluy, S.L, Spain). The crude glycerol was neutralized using sulfuric acid and most of the residual methanol was removed by vacuum distillation. Finally, the remaining material was centrifuged at 2600g and decanted to remove suspended solids. The final product was analyzed by 1 H-NMR in deuterated dimethylsulfoxide using N, N-dimethylformamide as internal standard. The product obtained was glycerol enriched up to approximately 90%.
    Nuclear magnetic resonance
    5 20 mg of the sample was placed in 1.5 mL of D2O or DMSO-d6 in an NMR tube of 5 mm outside diameter. The one-dimensional spectra were recorded on a Varian 400 AS spectrometer, at 400 MHz. The acquisition parameters were: spectral width 6402 Hz, relaxation time 15 s, number of spectra 128, time of
    10 acquisition of 4.09 s, pulse width 90 °. The experiments were carried out at 25 ° C. The spectra were acquired by Fourier transform and adjusted with a Gaussian function. A baseline correction was applied throughout the spectral range.
    Enthalpies of fusion and solidification
    15 The equipment used for thermophysical characterization was a DSC-822e (Mettler-Toledo) calorimeter. The mass of the sample used was about 15 mg per sample. The sample was placed in a 100 µl aluminum crucible under N2 flow of 80 ml min-1. The measurements were performed in dynamic mode taking into account the melting temperature (Tm)
    20 of the sample. A constant increase of 0.5 K min-1 was applied starting the study 10 K below the Tm of material until reaching 10 K above it. The STARe software of
    v.11.00 of Mettler-Toledo was used to evaluate the resulting DSC curves. The enthalpy of phase change and temperature were obtained by integrating the DSC heat flux signal response.
    25 Example 1. General procedure for the synthesis of esters of 2-chloro-1 (chloromethyl) ethyl (IV)
    OR
    OH
    image12 image13 Cl O CTMS R4 image14 R4 image15 + HO O
    OH
    image16 HO
    Cl
    (III) (VII) (IV)
    Carboxylic acid (III) (1 mmol), glycerol (VII) (184 mg, 2 mmol) and chlorotrimethylsilane (CTMS, 540 mg, 5 mmol) were added to a reaction vial provided with a PTFE plug. The mixture was heated at 80 ° C for 48 h. After cooling, an organic solvent (1 mL of a hydrocarbon solvent, such as hexane or pentane, or an ether such as diethyl ether, was added,
    image17
    image18
    image19
    (m, J = 9.5, 4.4 Hz, 1H), 4.20 - 4.12 (m, J = 15.4, 8.0 Hz, 6H), 1.81 - 1.68 (m , 4H), 1.29-1.17 (m, 4H), 0.86 (t, J = 7.4 Hz, 6H).
    Compound (XV) (R4 = (CH3) 3C-): 1H NMR (400 MHz, CDCl3) δ 10.53 (t, J = 1.4 Hz, 2H), 8.26 (t, J = 1.7 Hz, 2H), 7.22 (t, J = 1.8 Hz, 2H), 6.04 (tt, J = 8.0, 3.2 Hz, 1H), 5.10 (ddd, J = 17 , 3, 14.1, 5.7 Hz, 4H), 4.31-4.15 (m, 4H), 1.92-1.81 (m, 4H), 1.42-1.30 (m , 4H), 1.09 (s, J = 2.3 Hz, 9H), 0.94 (t, J = 7.4 Hz, 6H).
    Compound (XV) (R4 = CH3- (CH2) 14-): 1H NMR (400 MHz, CDCl3) δ 10.53 (t, J = 1.4 Hz, 2H), 8.26 (t, J = 1 , 7 Hz, 2H), 7.22 (t, J = 1.8 Hz, 2H), 6.04 (tt, J = 8.0, 3.2 Hz, 1H), 5.10 (ddd, J = 17.3, 14.1, 5.7 Hz, 4H), 4.31-4.15 (m, 4H), 2.36 (t, J = 7.5 Hz, 2H), 1.92 - 1.81 (m, 4H), 1.64 (q, J = 7.4 Hz, 2H), 1.42 - 1.30 (m, 4H), 1.37-1.20 (m, 24H) , 0.94 (t, J = 7.4 Hz, 6H), 0.91 0.84 (m, 3H).
    Compound (XV) (R4 = 1-naphthyl): 1H NMR (400 MHz, DMSO) δ 9.56 (s, 2H), 8.48-8.42 (m, J = 6.3, 3.4 Hz , 1H), 8.31 (d, J = 7.3 Hz, 1H), 8.25 (d, J = 8.2 Hz, 1H), 8.05 - 8.01 (m, J = 5, 9, 3.7 Hz, 1H), 7.99 (t, J = 1.6 Hz, 2H), 7.82 (t, J = 1.5 Hz, 2H), 7.64 - 7.55 ( m, 3H), 6.04 (tt, J = 8.7, 2.8 Hz, 1H), 4.92 (dd, J = 14.4, 2.7 Hz, 2H), 4.69 (dd , J = 14.4, 8.6 Hz, 2H), 4.12 (t, J = 7.0 Hz, 4H), 1.61-1.51 (m, 4H), 1.03-0, 92 (m, 4H), 0.59 (t, J = 7.4 Hz, 6H).
    Compound (XVI) (R3 = CH2 = CH-CO): 1H NMR (400 MHz, DMSO-d6) δ 9.24 (s, 2H), 7.83 (m, 2H), 7.78 (m, 2H ), 6.41 (dd, J ¼ 17.2, 1.3 Hz, 1H), 6.17 (dd, J ¼ 17.2, 10.5 Hz, 1H), 6.02 (dd, J ¼ 10.5, 1.3 Hz, 1H), 5.64-4.59 (m, 1H), 4.72-468 (m, 2H), 4.50-4.44 (m, 2H), 4 , 24 (q, J ¼ 7.3 Hz, 4H), 1.90 (t, J ¼ 7.6 Hz, 4H), 1.40 (m, 4H), 0.92 (t, J ¼ 7, 4 Hz, 6H). Example 6. General procedure for the synthesis of chloride and hexafluorophosphate 1- (2- (acyloxy) -3-chloropropan-1-yl) -3-butylimidazolium (XI)
    A mixture of a 2-chloro-1- (chloromethyl) ethyl (IV) ester (50 mmol) and N-butylimidazole (VIII) (50 mmol) was heated at 110 ° C for 20 h in a reactor under an argon atmosphere. The mixture was cooled to room temperature, toluene was added and a white solid precipitated with chloroform. The desired compound was recovered by silica gel column chromatography. The change of the chloride counterion by hexafluorophosphate is carried out by the same procedure described in example 5, with the only difference using a molar ratio of monoimidazolium chloride: potassium hexafluorophosphate 1: 1,2.
    Example 7. Fusion enthalpies and solidification of bisimidazolium salts and comparison with monoimidazolium salts.
    Bisimidazolium salts N N R3O N N R2 nA R1 (I)
    R1 R2R3nTOEnthalpy of fusion (kJ / kg)Enthalpy of solidification (kJ / kg)
    butylbutyl (CH3) 3CCO2Cl500310
    butylbutyl (CH3) 3CCO2PF6 -200150
    butylbutyl CH3 (CH2) 14CO2Cl900280
    butylbutyl CH3 (CH2) 14CO2PF6 -110100
    butylbutyl H2Cl400160
    butylbutyl 1-naphthyl-CO2Cl350200
    butylbutyl 1-naphthyl-CO2PF6 -180180
    butylbutyl CH2 = CH-CO2Cl650360
    butylbutyl CH2 = CH-CO2PF6 -250200
    Monoimidazolium salts Cl R3O N N nA-R1
    R1 R3nTO-Enthalpy of fusion (kJ / kg)Enthalpy of solidification (kJ / kg)
    butyl (CH3) 3CCOoneCl80fifty
    butyl (CH3) 3CCOonePF6 -70fifty
    5 The results show that all bisimidazolium salts of formula (I) studied have fusion enthalpies between 110 kJ / kg and 900 kJ / kg and solidification enthalpies between 100 kJ / kg and 360 kJ / kg, values that indicate an important thermal energy storage capacity, capacity in some cases much higher than
    10 current commercial products. In addition, the enthalpies of fusion and solidification of
    image20
    权利要求:
    Claims (1)
    [1]
    image 1
    image2
    image3
    image4
    image5
    类似技术:
    公开号 | 公开日 | 专利标题
    ES2543347T3|2015-08-18|Procedure for the preparation of fatty acid alkanolamides
    US20160280691A1|2016-09-29|Triazole intermediates useful in the synthesis of protected n-alkyltriazolecarbaldehydes
    ES2818736T3|2021-04-13|Aromatic fluorination method
    ES2611780A1|2017-05-10|Bisimidazolium salts for energy storage |
    JP2008001704A|2008-01-10|Process for producing glycerol carbonate ester
    PT2847183T|2017-10-02|Process for the preparation of triazole compounds
    ES2648662T3|2018-01-05|Process to produce a pyridazinone compound and production of intermediate compounds thereof
    US20160023984A1|2016-01-28|Manufacturing method of ester compound
    Kim et al.2013|Catalyst-free esterification of alcohols using 2-acyl-4, 5-dichloropyridazinones under microwave conditions
    Lauer et al.1937|The Rearrangement of Some Beta-Allyloxycrotonic Esters
    Han et al.2003|Preparation of 3‐| isoxazolecarboxylic esters
    EP3181545A1|2017-06-21|Method for producing triphenylbutene derivative
    JP2014185135A5|2016-03-10|
    US2335652A|1943-11-30|Vinyl esters
    AU2017232476B2|2019-10-03|Method for producing phenoxyethanol derivative
    RU2612259C1|2017-03-03|Method of producing n1, n3-bis | -2h-isoindole-1,3-diamines
    US2234374A|1941-03-11|Ether esters of halogenated salicylic acids
    JP2017071556A|2017-04-13|Manufacturing method of carboxylic acid prenyl and prenol using oxovanadium complex
    JP4831403B2|2011-12-07|Glycero compound having triple bond and film material containing the same
    GB1056268A|1967-01-25|Esters of 2-oxothiophen-3-carboxylic acids
    ES2596276T3|2017-01-05|Procedure for processing mixtures
    SU495312A1|1975-12-15|The method of obtaining derivatives-2 | -benzimidazole
    SU87649A1|1949-11-30|Method for producing mellitic acid ester |
    BR112018017117B1|2021-11-16|PRODUCTION METHOD FOR PHENOXYETHANOL DERIVATIVES
    JP3973398B2|2007-09-12|Thermally stable ferulic acid derivative, process for producing the same, and ultraviolet absorber containing the same as an active ingredient
    同族专利:
    公开号 | 公开日
    WO2017081343A1|2017-05-18|
    EP3375776A1|2018-09-19|
    ES2611780B1|2017-11-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2006076921A|2004-09-09|2006-03-23|Nof Corp|Polymerizable imidazole salt|
    KR20140040951A|2012-09-27|2014-04-04|롯데케미칼 주식회사|Method for separating aromatic compounds in naphtha using ionic liquids|
    法律状态:
    2017-11-15| FG2A| Definitive protection|Ref document number: 2611780 Country of ref document: ES Kind code of ref document: B1 Effective date: 20171115 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201531615A|ES2611780B1|2015-11-10|2015-11-10|Bisimidazolium salts for energy storage|ES201531615A| ES2611780B1|2015-11-10|2015-11-10|Bisimidazolium salts for energy storage|
    EP16812780.1A| EP3375776A1|2015-11-10|2016-11-08|Bisimidazolium salts for energy storage|
    PCT/ES2016/070790| WO2017081343A1|2015-11-10|2016-11-08|Bisimidazolium salts for energy storage|
    [返回顶部]