• 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:
    Rigid electric conductive gel composed of a pure ionic liquid, the decyl sulfate of 1-ethyl-3-methyl imidazolium [emim] [dso4] hydrated. Said rigid gel can be used, (as described or mixed with other additives such as solvents, inorganic salts or nanoparticles) in electrochemical devices (such as solar panels, batteries, capacitors, ...), electronic, sanitary, optical ..., and in all those where it is necessary to use electrically conductive pastes or creams. The main novelty is that the conductive rigid gel is formed by a pure hydrated compound that maintains its physical properties to the environment (that is, neither dries nor absorbs moisture). This has undoubted advantages over other conductive creams or pastes available in the market. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2553903A1
    申请号:ES201400476
    申请日:2014-06-10
    公开日:2015-12-14
    发明作者:Óscar CABEZA GRAS；Emilia Tojo Suárez；Miguel Vilas Aguete；Luis VARELA CABO
    申请人:Universidade de Santiago de Compostela；Universidade da Coruna；Universidade de Vigo；
    IPC主号:
    专利说明:

    OBJECT OF THE INVENTION The present invention relates to an ionic conductive material in the form of a rigid gel (it does not flow but is very deformable plastically). It is formed by a single chemical compound, the decyl sulfate of l-ethyl-3-methyl imidazolium, which although pure is a viscous liquid at temperature, pressure and environmental humidity, when hydrated with atmospheric humidity it goes into the state of rigid gel . This state remains stable between 15 ° C and 60 ° C. The object extends to the procedure for obtaining this substance and its possible uses.
    BACKGROUND OF THE INVENTION The combination in a material of the properties of charge transport of liquid ionic solutions with the mechanical properties of solids is very convenient in many electrochemical devices (batteries, supercapacitors, fuel cells ...) due to the great versatility of forms and the ease of handling of the solid state and the high ionic conductivity of liquids. To date, polymeric electrolytes (also called electrolyte polymers) have been used to obtain these materials, relatively novel materials in which an ionic conductor is immobilized inside a polymeric matrix. Within this category of compounds have been presented: - Dry electrolyte polymers, known since the early 70's, in which some salt is added in a polymer that acts as a solid solvent. Polymeric electrolyte gels or plasticized electro-lithium polymers, which combine an ionic liquid and a polymeric matrix, for example a block copolymer and a selectively soluble liquid in self-associated nano-structures. In this category
    ionogels based on the combination of molten salts have recently been introduced
    at room temperature (ionic liquids) with polymers or gelling agents (J. Le Bideau, L.
    Viau and A. Vioux, Ionogels, ionic liquid based hybrid materials, Chem. Soco Rev. 40,
    907-25 (2011)).
    Nº application26 / 12 / 2014F.OEPM22 / 12 / 2014F.Efectiva
    - Electrolytic composites, composites of electrolyte polymers or also composites of electrolytic ceramics, which include electrochemically inert compounds in the polymer matrices in order to look for increments of conductivity or stability in interfaces. A recent review of the state of the art of electrolyte polymers with abundant references in all the aforementioned systems can be found in Manuel Stephan, Review on gel polymer electrolytes for lithium batteries European Polymer Journal 42, 21-42 (2006). In all cases the presence of a polymer or a gelling material that provides the solid matrix of the system is necessary. Some of those currently used include polyethylene oxide, polyacetonitrile, polypropylene oxide, polyvinyl chloride, etc. To date, no pure compound was available, which is enough to hydrate it to the environment to combine the characteristics of high ionic conductivity of ionic liquids with mechanical properties of solids. It is at this point that the invention here communicated represents a qualitative advance in the state of the art. On the other hand, in the international patent No. PCT / EP2009 / 003373, by Wasserscheid et al. published on December 23, 2009, several compounds of the same family of alkyl sulphates ("alkyl sulfates") are collected here, although not exactly the one collected here, the decyl sulfate ("decyl sulfate"). The method for obtaining said compounds is also described.
    DESCRIPTION OF THE INVENTION The invention provides a new electrically conductive material with unique physical properties, it is highly deformable but does not flow. Furthermore, it has the advantage of being constituted by a single chemical compound which, when hydrated, confers the capacity to transport electric charges and the aforementioned mechanical properties. As it is constituted by a single compound, its preparation and characterization are easier than those similar currently existing, usually constituted by two or more compounds or components (including a gelling agent). In particular, said compound is l-ethyl-3-methylimidazolium decyl sulfate in the hydrated state, it is stable and easy to handle. Therefore, this new material will replace with advantage many of those already used in the different fields of the techniques mentioned above.
    Nº application26 / 12 / 2014F.OEPM22 / 12 / 2014F.Efectiva
    Thus, one aspect of the invention relates to an electrically conductive material comprising l-ethyl-3-methyl imidazolium decyl sulfate hydrate. The decyl sulfate of l-ethyl-3-methyl imidazolium is an ionic liquid based on the alkyl sulfate of l-ethyl-3-methyl imidazolium, in this case the alkyl chain consisting of ten carbon atoms (decyl sulfate). The electrically conductive material of the invention is in a state called rigid gel, does not flow but is very deformable plastically, at temperature, pressure and environmental humidity. The humidity moisturizes the decyl sulfate of l-ethyl-3-methyl imidazolium to a point from which its physical properties remain stable to the environment, its water content being dependent on the value of relative humidity (between 12% and 8% of the weight of the compound). This state of rigid gel maintains it between 15 ° C and 60 ° C, below freezes as an ionic crystal (with very low electrical conductivity) and above liquefies (flows). In a particular embodiment, the invention relates to an electrically conductive material consisting of l-ethyl-3-methyl imidazolium decyl sulfate hydrate. In a particular embodiment, the decyl sulfate hydrate of l-ethyl-3-methyl imidazolium is substantially pure. For the present invention, "substantially pure" means that said compound is in a higher proportion of at least 98%, preferably equal to or greater than 99%. The lack of purity of the compound prevents the appearance of the rigid gel state. In a particular embodiment, the electrical conductive material described above becomes in the form of a rigid gel upon hydration. The electrical conductive material of the invention can be combined and / or mixed with other components, such as, for example, salts, additives, etc. In a particular embodiment, the invention relates to a device comprising the electrical conductive material of the invention as described above. Optionally, the device may also comprise additives and / or salts. The electrical conductive material of the invention has application in electrochemical devices (such as solar panels, batteries, capacitors, ...), in electronics, in the sanitary field and in optical devices, due to its physical properties. Thus, another aspect of the invention relates to the use of the electrically conductive material, as described above, in electrochemical, electronic, optical and sanitary devices.
    Nº application26 / 12 / 2014F.OEPM22 / 12 / 2014F.Efectiva
    In another aspect, the invention relates to the process for the preparation of the electrically conductive material, as described above, which comprises a transesterification reaction between 1-decanol and 1-ethyl-3-methyl imidazolium ethyl sulfate in the presence of a acid. In a particular embodiment, the acid is selected from methane sulfonic acid and para-toluene sulfonic acid. In a particular embodiment, the reaction takes place between 20 ° C and 60 ° C. In a particular embodiment, the process further comprises a step prior to preparing the ethyl-1-ethyl-3-methyl imidazolium sulfate comprising the quatemization reaction of ethyl-1-ethyl-3-methyl imidazolium sulfate with diethyl sulfate. In another aspect, the invention relates to an electrically conductive material obtainable by a transesterification reaction between 1-decanol and 1-ethyl-3-methyl imidazolium ethyl sulfate in the presence of an acid.
    DESCRIPTION OF THE FIGURES Figure 1 is a synthetic scheme of the preparation of decyl sulfate of 1-ethyl-3-methyl imidazolium, represented in two stages: 1. Quatemization stage; 2. Transesterification stage.
    Below are examples that illustrate the invention but are not limiting thereof. Example 1. Obtaining 1-ethyl-3-methyl imidazolium ethyl sulfate [EMIM] [ES04]. Ethyl 1-ethyl-3-methyl imidazolium ethyl sulfate [EMIM] [ES04] was prepared by direct alkylation of 1-methyl imidazole (127 mmol) with diethyl sulfate (127 mmol) in toluene (50 ml). The [EMIM] [ES04] was obtained in the form of a colorless liquid with more than 99% purity and high yield (92%). The structure of [EMIM] [ES04] was confirmed by NMR_1 H and NMR _13 C spectroscopy whose data coincided fully with those described in the literature. Example 2. Obtaining 1-ethyl-3-methyl imidazolium decyl sulfate [EMIM] [DS04]. The [EMIm] [ES04] obtained in example 1, was transformed into [EMIm] [DS04] through a transesterification reaction in the following manner: on a mixture of 1-decanol (84 mmol) and [EMIm] [ ES04] (42 mmol) was added methane sulfonic acid (4.2 mmol) and the resulting mixture was allowed to stir at 40 ° C for 6-8 h. The ethanol formed in the course of the reaction was continuously evaporated by vacuum distillation. The progress of the reaction was followed by H NMR-1 spectroscopy. Once the reaction was complete, the mixture was neutralized with an aqueous solution of 0.5 M sodium hydroxide (8.5 ml) and the excess l-decanol was extracted with tetracycline. Butyl methyl ether (3 x 25 mL). After the last extraction, the solvent was
    Nº application26 / 12 / 2014F.OEPM22 / 12 / 2014F.Efectiva
    completely evaporated by heating under reduced pressure resulting in a semi-solid residue. After the addition of acetone (25 ml), the resulting mixture was maintained at -20 ° C for 12 h after which the formation of a white precipitate (sodium methanesulfonate) was observed which was separated by filtration. Finally, the filtrate was concentrated and subjected to stirring under high vacuum (0.2 Pa) for 12 h at a temperature of 70 ° C to eliminate remains of solvent and water. The [EMlm] [DS04] was obtained with more than 99% purity and high yield (97%) in the form of a very viscous and colorless liquid. l H NMR (400 MHz, CDCh, ppm): 9.56 [s, lH, H-2], 7.40 [dd, 2H, JI = 1.8 Hz, h = 9.0 Hz, H-4, H-5], 4.29 [ c, 2H, J = 7.4 Hz, NCH2CH3], 4.01 [m, 5H, OCH2 (CH2) 8CH3, NCH3], 1.64 [m, 2Hz, OCH2CH2 (CH2hCH3], 1.54 [t, 3H, J = 7.4 Hz, NCH2CH3 ], 1.31 [m, 14H, OCH2CH2 (CH2) 7CH3], 0.85 [t, 3H, J = 6.9 Hz, O (CH2) 9CH3] .3C NMR
    (100.6 MHz, CDCb, ppm): 136.8,123.8,122.1,67.5,45,0,36,2,31,8,29,6,29,5,29.4, 29.3, 29.2, 25.8, 22.5, 15.4, 14.0. MS electrospray (micrOTOF Focus) miz (%): 807 [(C6HllN) 3 (ClOH2104Sht (68), 460 [(C6HllNh (ClOH2104S) + lt (26), 459.2997 [(C6HllN) 2 (ClOH2104S) t (Cale. C22H43N404S: 459.3000, 100).
    Example 3 Obtaining l-ethyl-3-methyl imidazolium decyl sulfate hydrate [EMIM] [DS04]. The pure compound described above is left open to the environment, preferably extended, and after a few hours it has been hydrated. To accelerate the process, the compound can be introduced in a controlled atmosphere chamber, with air saturated with moisture. In a few minutes we will have the ionic fluid hydrated in the form of a rigid gel.
    At 25 oC of temperature the density of the final compound is 1050 kg / m3, its ionic conductivity is 2 S / m, while its viscosity is greater than 20 Pa · s.
    Nº application26 / 12 / 2014F.OEPM22 / 12 / 2014F.Efectiva
    DESCRIPTION OF A PREFERRED EMBODIMENT Obtaining 1-ethyl-3-methyl imidazolium decyl sulfate [EMIM] [DS04] 1-Ethyl-3-methyl imidazolium ethylsulfate [EMIM] [ES04] was prepared by direct alkylation of 1-methylimidazole (127 mmol) with diethyl sulfate (127 mmol) in toluene (50 ml). The [EMIM] [ES04] was obtained in the form of a colorless liquid with more than 99% purity and high yield (92%). The structure of [EMIM] [ES04] was confirmed by 1 H NMR and 13 C NMR spectroscopy whose data coincided fully with those described in the literature. The [EMIm] [ES04] obtained was transformed into [EMIm] [DS04] through a transesterification reaction according to a procedure previously described in the literature for the preparation of similar compounds and which has been slightly modified as follows: on a mixture of 1-decanol (84 mmol) and [EMIm] [ES04] (42 mmol) was added methanesulfonic acid (4.2 mmol) and the resulting mixture was allowed to stir at 40 ° C for 6-8.
    h. The ethanol formed in the course of the reaction was continuously evaporated by vacuum distillation. The progress of the reaction was followed by NMR spectroscopy) H. After the reaction was complete, the mixture was neutralized with an aqueous solution of 0.5 M sodium hydroxide (8.5 ml) and the excess 1-decanol was extracted with tert-butyl methyl ether (3 x 25 ml). After the last extraction, the solvent was completely evaporated by heating under reduced pressure resulting in a semi-solid residue. After the addition of acetone (25 ml), the resulting mixture was maintained at -20 ° C for 12 h after which the formation of a white precipitate (sodium methanesulfonate) was observed which was separated by filtration. Finally, the filtrate was concentrated and subjected to stirring under high vacuum (0.2 Pa) for 12 h at a temperature of 70 ° C to eliminate remains of solvent and water. The [EMlm] [DS04] was obtained with more than 99% purity and high yield (97%) in the form of a very viscous and colorless liquid. IH NMR (400 MHz, CDCh, ppm): 9.56 [s, lH, H-2], 7.40 [dd, 2H, JI = 1.8 Hz, h = 9.0 Hz, H-4, H-5], 4.29 [c , 2H, J = 7.4 Hz, NCH2CH3], 4.01 [m, 5H, OCH2 (CH2) sCH3, NCH3], 1.64 [m, 2Hz, OCH2CH2 (CH2) 7CH3], 1.54 [t, 3H, J = 7.4 Hz, NCH2CH3], 1.31 [m, 14H, OCH2CH2 (CH2) 7CH3], 0.85 [t, 3H, J = 6.9 Hz, O (CH2) 9CH3]. l3C NMR
    (100.6 MHz, CDCh, ppm): 136.8, 123.8, 122.1.67.5.45.0.36.2.31.8.29.6.29.5.29.4, 29.3, 29.2, 25.8, 22.5, 15.4, 14.0. MS electrospray (micrOTOF Focus) miz (%): 807 [(C6HIIN) 3 (CIOH2104S) 2r (68), 460 [(C6HIlN) 2 (CIOH2104S) + Ir (26), 459.2997 [(C6HIlN) 2 (CIOH2104S) t (Calc. For C22H43N404S: 459.3000,100).
    权利要求:
    Claims (4)
    [1]
    1. Ionic conductive substance in a rigid gel state composed of hydrated 1-ethyl-3-methyl imidazolium decyl sulfate characterized by not flowing but being highly plastically deformable. This state appears between 15 ° C and 60 ° C, below the rigid gel crystallizes forming a non-conductive crystalline solid, while above 60 ° C the rigid gel liquefies and flows.
    [2]
    2. Any mixture obtained from the previous compound to which any additive is added, in particular: ionic salts, nanoparticles and organic or inorganic solvents.
    [3]
    3. Use of decyl sulfate salt of 1-ethyl-3-methyl imidazolium [EMIm] [DS04] hydrated for any application.
    [4]
    Four. Procedure for obtaining the decyl sulfate of 1-ethyl-3-methyl imidazolium [EMIm] [DS04] hydrated described in claim 1, comprising the following steps:
    (to) Quatemization reaction between 1-methyl imidazole and diethyl sulfate in the presence of a solvent to generate 1-ethyl-3-methyl imidazolium ethyl sulfate [EMIM] [ES04l
    (b) Transformation of 1-ethyl-3-methyl imidazolium ethyl sulfate [EMIM] [ES04] into 1-ethyl-3-methyl imidazolium decyl sulfate [EMIM] [DS04] by treatment with 1-decanol by a transesterification reaction catalyzed with acid.
    (c) Hydration of [EMIM] [DS04] by exposure to ambient humidity.
    类似技术:
    公开号 | 公开日 | 专利标题
    Rengstl et al.2014|Low-melting mixtures based on choline ionic liquids
    Golding et al.2002|Methanesulfonate and p-toluenesulfonate salts of the N-methyl-N-alkylpyrrolidinium and quaternary ammonium cations: novel low cost ionic liquids
    Fukumoto et al.2006|Design and synthesis of hydrophobic and chiral anions from amino acids as precursor for functional ionic liquids
    KR101413775B1|2014-06-30|Fluoroalkane derivative, gelling agent and gel composition
    ES2628312T3|2017-08-02|Processes for preparing N-ethyl-2-methylpyridinium bromide and N-ethyl-3-methylpyridinium bromide
    Ning et al.2012|The physicochemical properties of some imidazolium-based ionic liquids and their binary mixtures
    KR101643698B1|2016-07-28|Safe battery solvents
    WO2007104144A1|2007-09-20|Compounds, ionic liquids, molten salts and uses thereof
    Chen et al.2015|Volumetric and viscosity properties of dicationic ionic liquids in | solutions at T= 298.15 K
    EP3275916B1|2021-12-15|Polymer, oxidized polymer, polymer composition, gel-type polymer composition, and use thereof
    ES2553903A1|2015-12-14|Ionic conductor in a rigid gel state |
    Jamehbozorg et al.2018|Evaluation of the effect of ionic-liquids as soluting-out agents on the solubility of carbohydrates in aqueous solutions
    JP5780484B2|2015-09-16|Ionic liquid
    Xu et al.2019|Volumetric and viscometric investigation of aqueous solution of [Bmim][BF4] from 288.15 to 318.15 K
    US8834743B2|2014-09-16|Dicarboxylate gemini surfactant that forms a lyotropic liquid crystal
    Mallet et al.2004|Crystal growth mechanism in a solution of hollow whiskers of molecular compounds
    JP6371157B2|2018-08-08|Ionic liquid, redox flow secondary battery electrolyte, redox flow secondary battery and salt
    KR20060120253A|2006-11-24|Crystal of oxacephem
    JP2004247252A|2004-09-02|Proton conducting material and proton conducting film using same
    JP2014080388A|2014-05-08|Ionic liquid
    US9079829B2|2015-07-14|Method of preparing powder of a solid carbazic acid derivative
    Gupta et al.2016|Role of reduced precursor and solvolytic reagent molar ratio on preparation and properties of ionogel
    JPWO2018193732A1|2020-03-12|Silanol compound and method for producing silanol compound
    Min et al.2020|Hydrogen halide-free synthesis of organohalides for organometal trihalide perovskite solar cells
    ES2652362B1|2018-11-13|SALT BLENDS TO DISSOLVE CELLULOSE
    同族专利:
    公开号 | 公开日
    ES2553903B2|2016-04-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2006111712A2|2005-04-20|2006-10-26|The Queen's University Of Belfast|Ionic liquids and uses thereof|CN109174176A|2018-08-01|2019-01-11|沈阳工业大学|Alkaline ionic liquid catalyst and preparation method thereof|
    法律状态:
    2016-04-28| FG2A| Definitive protection|Ref document number: 2553903 Country of ref document: ES Kind code of ref document: B2 Effective date: 20160428 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201400476A|ES2553903B2|2014-06-10|2014-06-10|Ionic conductor in a rigid gel state|ES201400476A| ES2553903B2|2014-06-10|2014-06-10|Ionic conductor in a rigid gel state|
    [返回顶部]