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WO2013146745A1 - Procédé de production de gel contenant un liquide ionique - Google Patents

Procédé de production de gel contenant un liquide ionique Download PDF

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WO2013146745A1
WO2013146745A1 PCT/JP2013/058710 JP2013058710W WO2013146745A1 WO 2013146745 A1 WO2013146745 A1 WO 2013146745A1 JP 2013058710 W JP2013058710 W JP 2013058710W WO 2013146745 A1 WO2013146745 A1 WO 2013146745A1
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ionic liquid
polymer
alkylene group
gel
group
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Japanese (ja)
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崇匡 酒井
雄一 鄭
充弘 柴山
健太 藤井
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University of Tokyo NUC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/3332—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/30—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type branched
    • C08G2650/32—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type branched dendritic or similar
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a polymer crosslinked gel containing an ionic liquid, an ionic liquid mixed solvent suitable for the production method, and an ionic liquid-containing gel obtained by the production method.
  • hydrogel which is a gel material containing a hydrophilic polymer having a network structure
  • Hydrogel has excellent water retention and biocompatibility characteristics, so it can be used not only for medical purposes such as sealing, adhesion prevention, drug delivery and contact lenses, but also for various applications such as sensors and surface coatings.
  • Is an expected material for example, Patent Documents 1 and 2).
  • Patent Documents 1 and 2 While it has excellent characteristics, it cannot be used for a wide range of practical purposes, or sufficient strength cannot be obtained, or the moisture contained in the gel evaporates over time and is lost for a long time. There was a problem that could not be done.
  • ionic liquids also called room temperature molten salts
  • room temperature molten salts are composed only of ions and are non-volatile and non-flammable despite being liquid in a wide temperature range including room temperature. It is known that it has the property of having From these characteristics, application to various fields including electrochemical devices such as lithium secondary batteries and capacitors, lubricants in machines, etc. is expected and research and development are being performed (for example, Patent Document 3).
  • Patent Document 3 For such applications, thinning of the ionic liquid is one important key, but no thin film formation reaction in the ionic liquid has been reported so far.
  • the reaction rate is controlled by controlling the hydrogen ion concentration in the reaction solvent.
  • the verification of reaction rate control in an ionic liquid has hardly been performed.
  • the present inventors have used a mixed solvent of a protic ionic liquid and an aprotic ionic liquid as a reaction solvent, so that a specific polymer solution is contained in the ionic liquid. It has been found that a crosslinking reaction (gelation reaction) can proceed only by mixing, whereby a polymer crosslinked gel containing an ionic liquid can be obtained directly. It has also been found that the reaction rate of the gelation reaction can be controlled by changing the ratio of the protic ionic liquid to the aprotic ionic liquid in the mixed solvent. Based on these findings, the present invention has been completed.
  • the present invention is a method for producing a polymer cross-linked gel containing an ionic liquid, the mixture comprising at least one kind of protic ionic liquid and at least one kind of aprotic ionic liquid.
  • the present invention relates to a production method characterized by crosslinking a polymer in a solvent.
  • the protonic ionic liquid is preferably an ionic liquid composed of a cation component selected from imidazolium-based, pyridinium-based, or primary ammonium.
  • the cation component of the protic ionic liquid is preferably 1-ethylimidazolium
  • the cation component of the aprotic ionic liquid is preferably 1-ethyl-3-methylimidazolium.
  • the combination of the protic ionic liquid and the aprotic ionic liquid is a combination of 1-ethylimidazolium bis (trifluoromethanesulfonyl) amide and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide.
  • the combination is selected from the group consisting of 1-ethylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium tetrafluoroborate.
  • the above polymer is preferably a polymer that can form a three-dimensional network structure by cross-linking each other.
  • the polymer comprises a first polymer having f nucleophilic functional groups in the side chain or terminal and a second polymer having g electrophilic functional groups in the side chain or terminal.
  • f + g is preferably 5 or more.
  • the polymer structure has a polyethylene glycol skeleton.
  • the polymer contains a compound represented by the following formula (I) and the following formula (II), and has a network structure by crosslinking the ends of the compound with an amide bond.
  • Is. (Here, in formula (I), n 11 to n 14 are the same or different and each represents an integer of 25 to 250, In the formula (I), R 11 to R 14 are the same or different and each represents a C 1 -C 7 alkylene group, a C 2 -C 7 alkenylene group, —NH—R 15 —, —CO—R 15 —, — R 16 —O—R 17 —, —R 16 —NH—R 17 —, —R 16 —CO 2 —R 17 —, —R 16 —CO 2 —NH—R 17 —, —R 16 —CO—R 17 —, or —R 16 —CO—NH—R 17 —, wherein R 15 represents a C 1 -C 7 alkylene group
  • n 21 to n 24 are the same or different and represent an integer of 20 to 250
  • R 21 to R 24 are the same or different and each represents a C 1 -C 7 alkylene group, a C 2 -C 7 alkenylene group, —NH—R 25 —, —CO—R 25 —, — R 26 —O—R 27 —, —R 26 —NH—R 27 —, —R 26 —CO 2 —R 27 —, —R 26 —CO 2 —NH—R 17 —, —R 26 —CO—R 27 —, or —R 26 —CO—NH—R 27 —, wherein R 25 represents a C 1 -C 7 alkylene group, R 26 represents a C 1 -C 3 alkylene group, and R 27 represents C 1 -C 5 alkylene group.
  • the present invention relates to a solvent for use in a polymer crosslinking reaction, comprising at least one or more protic ionic liquids and at least one or more aprotic ionic liquids.
  • a solvent for use in a polymer crosslinking reaction comprising at least one or more protic ionic liquids and at least one or more aprotic ionic liquids.
  • preferred embodiments of the protic ionic liquid and the aprotic ionic liquid in the solvent of the present invention are the same as described above.
  • the present invention relates to a polymer cross-linked gel containing an ionic liquid, wherein the polymer is mixed in a mixed solvent containing at least one protic ionic liquid and at least one aprotic ionic liquid. It relates to a gel obtained by cross-linking.
  • preferred embodiments of the protic ionic liquid and the aprotic ionic liquid are the same as described above.
  • species which forms the polymer crosslinked gel of this invention is the same as that of what was described above.
  • the present invention relates to a thin film comprising a polymer cross-linked gel containing the ionic liquid.
  • the crosslinking reaction can proceed only by mixing a specific polymer solution in the ionic liquid. It is possible to produce a polymer cross-linked gel containing an ionic liquid. This makes it possible to obtain a gel containing an ionic liquid by a simple process without performing a step of impregnating the ionic liquid after forming the gel once in an aqueous solution or the like.
  • the ratio of the protic ionic liquid to the aprotic ionic liquid in the mixed reaction solvent it is possible to control the reaction rate of the gelation reaction (that is, the gelation time). Therefore, it is very suitable when the gel is formed into a desired shape.
  • the gel when a device such as a gel thin film containing an ionic liquid is produced, the gel can be formed into an arbitrary shape from a fluid state by a simple process, and depending on the desired final device shape, etc. Since the flow state can be controlled, it is possible to produce a device such as a large amount of a uniform ionic liquid thin film.
  • the idea of controlling the reaction rate by the ratio of the protic ionic liquid and the aprotic ionic liquid is a novel one that has not been heretofore, and is not limited to the gelation reaction described above, and is a chemical reaction widely involving ionization of reactive species. Therefore, the usefulness of ionic liquids as a reaction solvent in general is demonstrated.
  • a polymer cross-linked gel having the characteristics of an ionic liquid while having the advantages of a conventional hydrogel.
  • a polymer having a network structure in combination with an ionic liquid sufficient strength can be obtained even in various applications, and a non-volatile ionic liquid is used as a solvent, so that the gel form is lost.
  • the gel form is lost.
  • the gel since a large amount of ionic liquid can be retained in the gel by using a polymer having a network structure, the gel has the excellent electrical conductivity, CO 2 absorbability, or flame retardant properties possessed by the ionic liquid. It becomes possible to add.
  • a highly transparent gel can be obtained.
  • a thin film material having the characteristics of the gel of the present invention can be provided, whereby not only the use of the conventional hydrogel but also the recovery and storage of CO 2 or lithium Applications can also be expected in the field of electrochemical devices such as ion secondary batteries.
  • FIG. 1 is a diagram showing a mechanism for controlling gelation time in an ionic liquid according to the present invention.
  • FIG. 2 is a graph showing the measurement results of the time dependency of the storage elastic modulus G ′ and the loss elastic modulus G ′′ in the gelation reaction using the ionic liquid mixed solvent of the present invention.
  • FIG. 3 is a graph showing the results of concentration dependence of the protic ionic liquid on the gelation time in the gelation reaction using the ionic liquid mixed solvent of the present invention.
  • FIG. 4 is a graph showing the results of a tensile test performed on the polymer crosslinked gel of the present invention.
  • the ionic liquid used as a reaction solvent in the present invention is a mixed solvent containing at least one kind of protic ionic liquid and at least one kind of aprotic ionic liquid.
  • protic ionic liquid HA + B ⁇ HB + A - is a ionic liquid synthesized by neutralization of the Bronsted acid represented by the reaction formula (HA) and Bronsted bases (B), Medium It is also called a Japanese ionic liquid.
  • aprotic ionic liquid means something other than these protic ionic liquids.
  • protic ionic liquid and aprotic ionic liquid used in the present invention is not limited, and known ones can be used.
  • the cationic species for example, primary (R 1) NH 3 + ), secondary (R 1 R 2 NH 2 + ), tertiary (R 1 R 2 R 3 NH + ), quaternary (R 1 R 2 R 3 R 4 N + ) chain ammonium Cation (wherein R 1 , R 2 , R 3 and R 4 are each independently a linear or branched alkyl group having 1 to 15 carbon atoms, or 1 carbon atom having one or more hydroxyl groups in the side chain) -15 linear or branched alkyl groups or phenyl groups) and cyclic ammonium cations.
  • Cyclic ammonium cations include oxazolium, thiazolium, imidazolium, pyrazolium, pyrrolium, furazanium, triazolium, pyrrolidinium, imidazolidinium, pyrazolidinium, pyrrolium, imidazolinium, pyrazolinium, pyrazinium, pyrimidinium, pyridazinium, piperidinium, piperidinium, morpholinium, morpholinium, And lithium and carbazolium.
  • a chain phosphonium cation (R 5 R 6 R 7 P + and R 5 R 6 R 7 R 8 P + ), a chain sulfonium cation (R 9 R 10 R 11 S + ) (in the formula, , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group) and a cyclic sulfonium cation.
  • the cyclic sulfonium cation include thiophenium, thiazolinium, and thiopyranium.
  • anionic species include inorganic acid ions such as phosphoric acid, sulfuric acid, and carboxylic acid, and fluorine ions.
  • fluorine-based anions include tetrafluoroborate (BF 4 ⁇ ), hexafluoroborate (BF 6 ⁇ ), hexafluorophosphate (PF 6 ⁇ ), hexafluoroarsenate (AsF 6 ⁇ ), trifluoromethanesulfonate (CF 3 SO 3 ⁇ ), bis (fluorosulfonyl) amide ((FSO 2 ) 2 N ⁇ ), bis (trifluoromethanesulfonyl) amide ((CF 3 SO 2 ) 2 N ⁇ ), bis (trifluoroethanesulfonyl) amide ( And (CF 3 CF 2 SO 2 ) 2 N ⁇ ) and tris (trifluoromethanesulfonylmethide) ((CF 3 SO 2 ) 3 C
  • the protic ionic liquid can be used as long as proton transfer can occur by the acid-base reaction, and is not particularly limited.
  • an imidazolium-based cation component examples thereof include an ionic liquid having a pyridinium-based cation component or a primary ammonium cation component.
  • it is an ionic liquid comprising an imidazolium-based or pyridinium-based cation component.
  • aprotic ionic liquid any combination of the above cationic species and anionic species can be used, but it is preferable to have a skeleton similar to the protic ionic liquid.
  • the cation component of the protic ionic liquid is 1-alkylimidazolium, and the cation component of the aprotic ionic liquid is 1-alkyl-3-methylimidazolium.
  • the cation component of the protic ionic liquid may be a primary ammonium cation, and the cation component of the aprotic ionic liquid may be a quaternary ammonium cation.
  • the cationic component of the protic ionic liquid is 1-ethylimidazolium, and the cationic component of the aprotic ionic liquid is 1-ethyl-3-methylimidazolium.
  • a combination of a protic ionic liquid and an aprotic ionic liquid include a combination of 1-ethylimidazolium bis (trifluoromethanesulfonyl) amide and 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, Alternatively, a combination of 1-ethylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium tetrafluoroborate can be given. It is also possible to use a combination of a plurality of types of protic ionic liquids and aprotic ionic liquids.
  • ionic liquids can be prepared by methods well known in the art.
  • the polymer used in the present invention is a polymer that is soluble in an ionic liquid and can contain an ionic liquid by forming a gel by a gelation reaction (crosslinking reaction or the like) in the ionic liquid.
  • gel generally refers to a dispersion having high viscosity and loss of fluidity.
  • a polymer that can form a network structure for containing an ionic liquid by cross-linking each other, particularly a three-dimensional network structure is preferable.
  • Such a polymer typically includes a polymer species having a plurality of polyethylene glycol skeleton branches, and a polymer species having four polyethylene glycol skeleton branches is particularly preferable.
  • polymers other than the polyethylene glycol skeleton can be used as long as they can be cross-linked to form a uniform network structure network to form a gel.
  • a polymer having a vinyl skeleton such as methyl methacrylate can also be used.
  • the polymer comprises a first polymer having f nucleophilic functional groups at the side chain or terminal and g electrophilic functional groups at the side chain or terminal.
  • a means for reacting and crosslinking two kinds of polymer species of the second polymer having ⁇ is preferable.
  • f + g is preferably 5 or more. These functional groups are more preferably present at the terminal.
  • f and g are 4 and f + g is 8 as in the compounds represented by formulas (I) and (II) described later.
  • it is preferable in that a uniform network structure network is obtained.
  • the terminal nucleophilic functional group is preferably an amino group.
  • a nucleophilic functional group other than an amino group can be used as the functional group as long as a cross-linking having a high-strength steric structure can be obtained.
  • examples of such a nucleophilic functional group include —SH or —CO 2 PhNO 2 (Ph represents an o-, m-, or p-phenylene group).
  • a nuclear functional group can be used as appropriate.
  • the terminal electrophilic functional group is preferably an N-hydroxy-succinimidyl (NHS) group.
  • active ester groups having electrophilicity may be used. Examples of such an active ester group include a sulfosuccinimidyl group, a maleimidyl group, a phthalimidyl group, an imidazolyl group, and a nitrophenyl group, and those skilled in the art can appropriately use known active ester groups.
  • the functional groups may be the same or different, but are preferably the same. By having the same functional group, the reactivity with the nucleophilic functional group becomes uniform, and it becomes easy to obtain a high-strength gel having a uniform three-dimensional structure.
  • polymer species having a nucleophilic functional group at the terminal are, for example, represented by the following formula (I) having four polyethylene glycol skeleton branches and an amino group at the terminal. Compounds.
  • R 11 to R 14 are the same or different and each represents a C 1 -C 7 alkylene group, a C 2 -C 7 alkenylene group, —NH—R 15 —, —CO—R 15 —, —R 16 —O—R 17 —, —R 16 —NH—R 17 —, —R 16 —CO 2 —R 17 —, —R 16 —CO 2 —NH—R 17 —, —R 16 —CO—R 17 —, Or —R 16 —CO—NH—R 17 —, wherein R 15 represents a C 1 -C 7 alkylene group, R 16 represents a C 1 -C 3 alkylene group, and R 17 represents C It shows the 1 -C 5 alkylene group. )
  • n 11 to n 14 may be the same or different from each other. As the values of n 11 to n 14 are closer, a uniform three-dimensional structure can be obtained and the strength becomes higher. For this reason, in order to obtain a highly strong gel, it is preferable that it is the same. When the value of n 11 to n 14 is too high, the gel strength is weakened, and when the value of n 11 to n 14 is too low, the gel is hardly formed due to steric hindrance of the compound. Therefore, n 11 to n 14 include integer values of 25 to 250, preferably 35 to 180, more preferably 50 to 115, and particularly preferably 50 to 60. The molecular weight is 5 ⁇ 10 3 to 5 ⁇ 10 4 Da, preferably 7.5 ⁇ 10 3 to 3 ⁇ 10 4 Da, and more preferably 1 ⁇ 10 4 to 2 ⁇ 10 4 Da.
  • R 11 to R 14 are linker sites that connect the functional group and the core portion.
  • R 11 to R 14 may be the same or different, but are preferably the same in order to produce a high-strength gel having a uniform three-dimensional structure.
  • R 11 to R 14 are a C 1 -C 7 alkylene group, a C 2 -C 7 alkenylene group, —NH—R 15 —, —CO—R 15 —, —R 16 —O—R 17 —, —R 16 —NH—R 17 —, —R 16 —CO 2 —R 17 —, —R 16 —CO 2 —NH—R 17 —, —R 16 —CO—R 17 —, or —R 16 —CO—NH— R 17 -is shown.
  • R 15 represents a C 1 -C 7 alkylene group.
  • R 16 represents a C 1 -C 3 alkylene group.
  • R 17 represents a C 1 -C 5 alkylene group.
  • C 1 -C 7 alkylene group means an alkylene group having 1 to 7 carbon atoms which may have a branch, and is a straight chain C 1 -C 7 alkylene group or one or two A C 2 -C 7 alkylene group having 2 or more branches (having 2 or more and 7 or less carbon atoms including branches) is meant.
  • Examples of C 1 -C 7 alkylene groups are a methylene group, an ethylene group, a propylene group and a butylene group.
  • C 1 -C 7 alkylene groups are —CH 2 —, — (CH 2 ) 2 —, — (CH 2 ) 3 —, —CH (CH 3 ) —, — (CH 2 ) 3 —, — ( CH (CH 3 )) 2 —, — (CH 2 ) 2 —CH (CH 3 ) —, — (CH 2 ) 3 —CH (CH 3 ) —, — (CH 2 ) 2 —CH (C 2 H 5 )-,-(CH 2 ) 6 -,-(CH 2 ) 2 -C (C 2 H 5 ) 2- , and-(CH 2 ) 3 C (CH 3 ) 2 CH 2- .
  • the “C 2 -C 7 alkenylene group” is an alkenylene group having 2 to 7 carbon atoms in the form of a chain having one or two or more double bonds in the chain or having a branched chain. And a divalent group having a double bond formed by removing 2 to 5 hydrogen atoms of adjacent carbon atoms from an alkylene group.
  • polymer species having an electrophilic functional group at the terminal include, for example, four polyethylene glycol skeleton branches and an N-hydroxy-succinimidyl (NHS) group at the terminal.
  • polymer species having an electrophilic functional group at the terminal include, for example, four polyethylene glycol skeleton branches and an N-hydroxy-succinimidyl (NHS) group at the terminal.
  • NHS N-hydroxy-succinimidyl
  • n 21 to n 24 may be the same or different. The closer the values of n 21 to n 24 are, the more preferable the hydrogel can have a uniform three-dimensional structure and high strength, and the same is preferable. If the value of n 21 to n 24 is too high, the gel strength is weakened. If the value of n 21 to n 24 is too low, the gel is difficult to be formed due to steric hindrance of the compound. Therefore, n 21 to n 24 may be integer values of 5 to 300, preferably 20 to 250, more preferably 30 to 180, still more preferably 45 to 115, and even more preferably 45 to 55.
  • the molecular weight of the second four-branched compound of the present invention is 5 ⁇ 10 3 to 5 ⁇ 10 4 Da, preferably 7.5 ⁇ 10 3 to 3 ⁇ 10 4 Da, and 1 ⁇ 10 4 to 2 ⁇ . 10 4 Da is more preferable.
  • R 21 to R 24 are linker sites that connect the functional group and the core portion.
  • R 21 to R 24 may be the same or different, but are preferably the same in order to produce a high-strength gel having a uniform three-dimensional structure.
  • R 21 to R 24 are the same or different and each represents a C 1 -C 7 alkylene group, a C 2 -C 7 alkenylene group, —NH—R 25 —, —CO—R 25 —, —R 26 —O—R 27 —, —R 26 —NH—R 27 —, —R 26 —CO 2 —R 27 —, —R 26 —CO 2 —NH—R 17 —, —R 26 —CO—R 27 —, Or —R 26 —CO—NH—R 27 — is shown.
  • R 25 represents a C 1 -C 7 alkylene group.
  • R 26 represents a C 1 -C 3 alkylene group.
  • R 27 represents a C 1 -C 5 alkylene group.
  • (3-1) Gelation step As a representative example of the gelation reaction step in the present invention, a) A desired amount of a protic ionic liquid is added to the aprotic ionic liquid to prepare a mixed solvent of the ionic liquid (here, even when a plurality of aprotic ionic liquids or protic ionic liquids are used, Similarly, a mixed solvent can be prepared), b) preparing a plurality of polymer solutions in which a desired polymer species is dissolved in the mixed solvent; c) A step of stirring and mixing the polymer solution.
  • step b a mixed solvent containing the polymer species of formula (I) (“first solution”) and formula (II)
  • a mixed solvent containing the polymer species (“second solution”) is prepared, and these are mixed in step c).
  • the mixing step c the step of adding and mixing the second solution to the first solution, the step of adding and mixing the first solution to the second solution, the first solution and the second solution And a step of mixing with the above solution.
  • the addition speed, mixing speed, and mixing ratio of the first solution or the second solution are not particularly limited, and can be adjusted as appropriate by those skilled in the art. It will be apparent that even when three or more polymer species are used, corresponding polymer solutions can be prepared in the same manner and mixed as appropriate.
  • a two-component mixing syringe as disclosed in International Publication No. WO2007 / 083522 pamphlet can be used.
  • the temperature of the two liquids at the time of mixing is not particularly limited, and is a temperature range that is equal to or higher than the melting point of the ionic liquid that is the solvent and lower than the temperature at which the cationic species or anionic species constituting the ionic liquid decomposes, May be melted and the temperature of each liquid may be fluid.
  • the temperature of the solution when mixing may be in the range of 1 ° C. to 100 ° C.
  • the temperature of the two liquids may be different, but the same temperature is preferable because the two liquids are easily mixed.
  • the concentration of the polymer species in the solution can be appropriately changed according to the type of the polymer or ionic liquid.
  • the polymer concentration in the mixed solvent is Examples include 10 mg / mL to 500 mg / mL. If the polymer concentration is too low, the gel strength becomes weak, and if the polymer concentration is too high, the gel structure becomes non-uniform and the gel strength becomes weak. Therefore, 20 to 400 mg / mL is preferable, 50 mg / mL to 300 mg / mL is more preferable, and 100 to 200 mg / mL is more preferable.
  • the polymer species of formula (I) and formula (II) can be mixed in a molar ratio of 0.5: 1 to 1.5: 1. Since the functional groups of the polymer species (ie amino groups and N-hydroxy-succinimidyl groups) can each react 1: 1, the mixing molar ratio is preferably closer to 1: 1, but in order to obtain a high strength gel Is particularly preferably 0.8: 1 to 1.2: 1.
  • the amino group is in a cationic state (—NH 3+ ) and tends to repel each other, and the cationic amino group reacts with the N-hydroxy-succinimidyl group. This is not preferable because the properties are lowered.
  • protons are supplied to the solution and the abundance ratio of -NH 3+ groups is adjusted to perform a crosslinking reaction and gelation at a desired reaction rate.
  • a protic ionic liquid for example, it is preferable to maintain a non-cationic amino group capable of reacting with an N-hydroxy-succinimidyl group at 5% or less in the solution in order to produce a uniform and strong hydrogel.
  • Fig. 1 shows the principle of reaction control described above from the viewpoint of chemical reaction kinetics.
  • Formula (1) in FIG. 1 represents a cross-linking reaction formula of a polymer by taking an amide group formation between an amino group and an N-hydroxy-succinimidyl group as an example.
  • the neutral amino group (—NH 2 ) is involved in the reaction, and the cationic amino group (—NH 3+ ) is not involved.
  • the abundance ratio of —NH 2 in the solution depends on the acid dissociation equilibrium (acid dissociation constant Ka).
  • the protic ionic liquid in the solution has a self-dissociation equilibrium of the formula (2) (where “C 2 ImH + ” represents a 1-ethylimidazolium cation).
  • C 2 ImH + represents a 1-ethylimidazolium cation.
  • X ⁇ that is a constituent anion of the ionic liquid is a strong acid
  • the concentration [HX] of HX can be regarded as the proton concentration [H + ]. Therefore, the proton concentration in the solution can be adjusted by the amount of the protonic ionic liquid added.
  • the abundance ratio of —NH 2 in the above formula (1) depends on the proton concentration [H + ] in the solution, as is clear from the equation of the acid dissociation constant Ka, and when [H + ] increases, 2 concentration (existence ratio) is in a relationship of increasing. Therefore, the reaction rate of amide bond formation (gelation) can be controlled by adding a protic ionic liquid.
  • This reaction control is very useful in that the fluid state until the gel solidifies can be appropriately controlled because the fluid state of the gel can be controlled according to the polymer type to be used, the desired final processing shape, and the like. is there
  • X ⁇ that is a constituent anion of an ionic liquid is a strong acid, and thus does not become a conjugate base that stabilizes protons. Therefore, it is difficult for the acid (HX) composed of X to coexist with the aprotic ionic liquid. Therefore, the control of the reaction rate is an action obtained only by using a protic ionic liquid.
  • a gel-like composition of a desired shape can be processed by controlling the gelation reaction.
  • the shape is preferably a thin film. Therefore, as a method for obtaining the gel thin film of the present invention, any method known in the art can be used.
  • a thin film containing an ionic liquid can be obtained by a technique such as coating on a flat substrate such as glass.
  • the gelation time is preferably 20 to 30 minutes.
  • TAPEG synthesis THPEG (0.1935 mmol, 3.87 g, 1.0 equiv) was dissolved in benzene, lyophilized, dissolved in 62 mL of THF, and triethylamine (TEA) (0.1935 mmol, 3.87 g, 1.0 equiv) was added. . To another eggplant flask, 31 mL of THF and methanesulfonyl chloride (MsCl) (0.1935 mmol, 3.87 g, 1.0 equiv) were added and placed in an ice bath.
  • TFA triethylamine
  • a THF solution of MsCl was added dropwise to a THF solution of THPEG and TEA over about 1 minute, stirred in an ice bath for 30 minutes, and then stirred at room temperature for 1 hour and a half. After completion of the reaction, it was reprecipitated in diethyl ether, and the precipitate was taken out by filtration. Furthermore, it wash
  • TAPEG TAPEG
  • n 11 to n 14 were 50 to 60 when the molecular weight of TAPEG was about 10,000 (10 kDa), and 100 to 115 when the molecular weight was about 20,000 (20 kDa).
  • TNPEG THPEG (0.2395 mmol, 4.79 g, 1.0 equiv) was dissolved in THF, 0.7 mol / L glutaric acid / THF solution (4.790 mmol, 6.85 mL, 20 equiv) was added, and Ar was present for 6 hours. Stir. After completion of the reaction, it was added dropwise to 2-propanol and centrifuged 3 times. The obtained white solid was transferred to a 300 mL eggplant flask, and the solvent was distilled off under reduced pressure using an evaporator. The residue was dissolved in benzene, and the insoluble material was removed by filtration.
  • Tetra-PEG-COOH was dissolved in THF, and N-hydrosuccinamide (2.589 mmol, 0.299 g, 12 equiv), N, N′-diisopropylsk Cinamide (1.732 mmol, 0.269 mL, 8.0 equiv) was added, and the mixture was stirred with heating at 40 ° C. for 3 hr. After completion of the reaction, the solvent was distilled off under reduced pressure using an evaporator.
  • TNPEG TNPEG as a white solid.
  • the chemical formula of the prepared TNPEG is shown in Formula (IIa).
  • n 21 to n 24 were 45 to 55 when the molecular weight of TNPEG was about 10,000 (10 k), and 90 to 115 when the molecular weight was about 20,000 (20 k).
  • 1-methylimidazole (Wako Pure Chemical Industries) was purified by distillation, and ethyl bromide (Wako Pure Chemical Industries) and lithium bis (trifluoromethanesulfonyl) amide (Wako Pure Chemical Industries) were used unpurified.
  • the produced LiBr and unreacted substances were removed by extraction with water, and a small amount of remaining impurities were removed by activated carbon chromatography. Thereafter, water was removed with a freeze dryer. Using 1 H-NMR, it was confirmed that a high-purity ionic liquid could be synthesized, and the water content was confirmed to be 100 ppm or less by a Karl Fischer moisture meter.
  • 1-Ethylimidazole (C 2 Im, Wako Pure Chemical Industries, Ltd.) was purified by distillation, and water was removed by molecular sieves. Trifluoromethanesulfonimide (HTFSA, Wako Pure Chemical Industries) was used unpurified. The mixture was mixed in a glove box under an argon atmosphere and stirred for 24 hours to react. After synthesis, moisture was removed with a freeze dryer. Using 1 H-NMR, it was confirmed that a high-purity ionic liquid could be synthesized, and the water content was confirmed to be 115 ppm by a Karl Fischer moisture meter.
  • HTFSA Trifluoromethanesulfonimide
  • the time at the point where G ′ and G ′′ intersect for each protic ionic liquid concentration is defined as the gel time.
  • the gel time when the concentration of the protic ionic liquid is 1.9 mM is It was 13 minutes, 35 minutes for 2.4 mM and 84 minutes for 2.5 mM.
  • a tensile test was performed on the gel of the present invention produced from a mixed solvent of [C 2 mIm + ] [TFSA ⁇ ] and [C 2 ImH + ] [TFSA ⁇ ].
  • TAPEG and TNPEG having a molecular weight of 10 k and a concentration of 5.0 mM were gelled using two mixed solvents in which the concentration of [C 2 ImH + ] [TFSA ⁇ ], which is a protic ionic liquid, was 12 mM and 18 mM.
  • the obtained gel was formed into a 1 ⁇ 5 ⁇ 20 mm strip shape to obtain a test sample.
  • the tensile tester used was SHIMADZU EZ-L 50N, and the measurement was performed under the condition of a tensile speed of 1 mm ⁇ s ⁇ 1 . It pulled until it broke from natural length, and the stress was measured.
  • Thin film production Using a mixed solvent of [C 2 mIm + ] [TFSA ⁇ ] and [C 2 ImH + ] [TFSA ⁇ ] as a solvent, the concentration of [C 2 ImH + ] [TFSA ⁇ ] is 12 mM, the molecular weight is 10 k, the concentration 5.0 mM TAPEG and TNPEG were used. After mixing two liquids of TAPEG and TNPEG solution and stirring sufficiently, the bubbles were removed through a filter having a pore size of 5.0 ⁇ m, and then a thin film having a thickness of 200 ⁇ m and a length and width of 10 ⁇ 10 cm was prepared using a 200 ⁇ m spacer. The obtained film could be used as a self-supporting film.

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JP2015137430A (ja) * 2014-01-20 2015-07-30 国立大学法人福井大学 ゲル繊維およびその不織布
EP3352272A3 (fr) * 2018-04-16 2018-08-15 High Tech Battery Inc. Électrolyte liquide ionique dans un dispositif de stockage d'énergie et son procédé de fabrication
US10122049B2 (en) 2014-02-06 2018-11-06 Gelion Technologies Pty Ltd Gelated ionic liquid film-coated surfaces and uses thereof
CN115466355A (zh) * 2022-09-30 2022-12-13 华中科技大学 一种多功能导电离子凝胶、制备方法及其应用
CN116364330A (zh) * 2023-03-01 2023-06-30 中科融志国际科技(北京)有限公司 一种疏水性电热除冰离子凝胶及其制备方法和用途

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WO2024209977A1 (fr) * 2023-04-07 2024-10-10 東京エレクトロン株式会社 Partie de support de substrat, dispositif de traitement de substrat et procédé de fabrication de partie de support de substrat

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CN115466355A (zh) * 2022-09-30 2022-12-13 华中科技大学 一种多功能导电离子凝胶、制备方法及其应用
CN115466355B (zh) * 2022-09-30 2023-10-24 华中科技大学 一种多功能导电离子凝胶、制备方法及其应用
CN116364330A (zh) * 2023-03-01 2023-06-30 中科融志国际科技(北京)有限公司 一种疏水性电热除冰离子凝胶及其制备方法和用途

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