JP2006302639A - Fuel supply device for fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel supply device for a fuel cell capable of safely conveying fuel for the fuel cell and simply supplying fuel to the fuel cell. <P>SOLUTION: The fuel supply device 1 for the fuel cell is equipped with a fuel housing part 2 and a flow means 3 continuously installed to the fuel housing part 2. The upper surface and the lower surface of the fuel housing part 2 are covered with liquid permeable sheets 4, 4A, and the inside is filled with a methanol clathrate compound 5. The flow means 3 is constituted by fitting a push button 7 to the top of a sponge 6 containing water so as to be capable of pressing the sponge 6. When the push button 7 is pressed, the sponge 6 is shrunk, water is supplied to the fuel housing part 2 through the water permeable sheet 4 to form a fuel aqueous solution. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an apparatus for supplying fuel to a fuel cell.

A solid polymer electrolyte fuel cell has a solid electrolyte membrane such as a perfluorosulfonic acid membrane as an electrolyte, and a fuel electrode and an oxidant electrode are joined to both sides of the membrane. Hydrogen or methanol is used for the anode and oxygen is used for the cathode. Is a device that generates electricity through an electrochemical reaction. The electrochemical reaction that occurs at each electrode is as follows:
CH ₃ OH + H ₂ O → 6H ⁺ + CO ₂ + 6e ⁻ [1]
And at the cathode,
3/2 O ₂ + 6H ⁺ + 6e ⁻ → 3H ₂ O [2]
It is. In order to cause this reaction, both electrodes are composed of a mixture of carbon fine particles carrying a catalyst material and a solid polymer electrolyte.

  In such a solid polymer electrolyte fuel cell, when methanol is used as the fuel, the methanol supplied to the anode reaches the catalyst through the pores in the electrode, and the methanol is decomposed by the catalyst. Electrons and hydrogen ions are generated by the reaction of reaction formula [1]. The hydrogen ions reach the cathode through the electrolyte in the anode and the solid electrolyte membrane between the electrodes, react with oxygen supplied to the cathode and electrons flowing from the external circuit, and water is formed as in the above reaction formula [2]. Arise. On the other hand, electrons emitted from methanol are led to the external circuit through the catalyst carrier in the anode, and flow into the cathode from the external circuit. As a result, in the external circuit, electrons flow from the anode to the cathode and electric power is taken out.

  This direct methanol fuel cell using methanol as a fuel has a high possibility of being applicable as a portable small fuel cell, and in recent years, development has been activated as a next-generation secondary battery such as a portable computer or a mobile phone.

However, since the fuel of the direct methanol fuel cell uses methanol as it is in a liquid state, it is highly dangerous and has many handling problems. As a method of safely storing such fuel, a method of using a fuel as a molecular compound (see Patent Document 1), a method of absorbing and gelling a polymer (see Patent Document 2), and a fatty acid ester of a polyhydric alcohol And the like (see Patent Document 3) have been reported. In addition, as a method for releasing fuel cell fuel from those fuel cell fuels having a stable composition, it is reported that water is passed through the fuel composition to release it.
International Publication No. 2004/000857 Pamphlet JP 2004-127659 A Japanese Patent Laid-Open No. 8-231970

  However, in the fuel discharge devices that have been reported in the past, the water that flows through the container containing the fuel composition for the fuel cell exists as a liquid, and the water may leak.

  An object of the present invention is to provide a fuel supply device for a fuel cell that can safely carry the fuel for the fuel cell and can easily supply the fuel to the fuel cell.

  The fuel supply device for a fuel cell according to the present invention includes a fuel storage portion in which a liquid fuel component is fixed, and a fluidizing means for causing the fuel in the fuel accommodation portion to flow. The liquid fuel component can be supplied to the fuel cell (claim 1). As a result, the liquid fuel component can be carried and stored in a solid state. Further, when the fuel cell is in operation, the liquid fuel component can be flowed by the flow means and supplied to the fuel cell.

  The fuel storage unit stores a fuel composition for a fuel cell that is released from the fuel for the fuel cell upon contact with water, the flow means is a moisture supply device, and the fuel storage device is supplied from the moisture supply device. By supplying water to the unit, an aqueous solution of the fuel for the fuel cell is created, and the aqueous fuel can be supplied to the fuel cell.

  The volume of the fuel storage section can be increased or decreased, and the fuel storage section is filled with microcapsules that store fuel cell fuel, and the flow means is a pressing body that changes the volume of the fuel storage section. If the volume of the fuel storage portion is reduced by the pressing body, the microcapsule may be broken to release the fuel cell fuel so that the fuel cell fuel can be supplied to the fuel cell.

  Further, the fuel storage part can be increased or decreased in volume, and the fuel composition for the fuel cell, which is released from the fuel cell fuel by contacting the fuel storage part with water, and the microcapsule containing the water And the flow means is a pressing body that changes the volume of the fuel storage section. When the volume of the fuel storage section is reduced by the pressing body, the microcapsule is damaged and water leaks. Then, an aqueous solution of the fuel for the fuel cell is prepared, and pressure can be supplied to the fuel cell in the aqueous fuel (claim 4).

  In such a fuel cell fuel supply device (claims 1 to 4), the fuel storage section may have a liquid fuel absorber (claim 5).

  Moreover, in such a fuel cell fuel supply device (Claims 1 to 5), the fuel cell fuel is one selected from the group consisting of alcohols, ethers, hydrocarbons, and acetals. Or 2 or more types can be used (Claim 6).

  In the fuel cell fuel supply apparatus of the present invention, the liquid fuel component is fixed in the fuel storage portion, and means for fluidizing the fixed liquid fuel component is separately provided. No liquid leaks from the part. By absorbing water into the fuel storage section, the fuel cell fuel can be easily released from the fuel composition containing the fuel cell fuel without requiring a heating device or heating energy.

  Therefore, it is possible to safely and stably store a fuel cell fuel that is difficult to handle as a fuel composition containing the fuel cell fuel, and then easily and inexpensively extract the fuel cell fuel from the fuel composition. .

  Of the fuels for fuel cells, the methanol stock solution corresponds to the deleterious substance of the Poisonous and Deleterious Substances Control Law, and it must be handled with great care, such as equivalent to the dangerous substance class 4, and has a high concentration. Methanol is usually used as an aqueous solution of about 10 to 30% by mass when methanol is used as a fuel because of problems such as corrosion. Therefore, it has been proposed as a general method to carry a cartridge of methanol aqueous solution, but preventing leakage of the aqueous solution has been a big problem. In the present invention, when the fuel composition is used, the fuel is brought into contact with water, and the fuel in the fuel composition is released into the water, so that the fuel can be supplied to the fuel cell as an aqueous solution having an appropriate concentration. .

Hereinafter, embodiments will be described with reference to the drawings.
FIG. 1 is a perspective view showing a fuel supply device for a fuel cell according to a first embodiment of the present invention, and FIG. 2 is a longitudinal sectional view.

  1 and 2, the fuel supply device 1 for a fuel cell includes a fuel storage portion 2 and a flow means 3 provided so as to be connected to the storage portion 2. The fuel storage unit 2 has an upper surface and a lower surface covered with the liquid permeable sheets 4 and 4 </ b> A, and is filled with a methanol clathrate compound 5. As described above, in the present embodiment, methanol, which is a liquid fuel component, is fixed as an inclusion compound and can be safely carried. Further, the flow means 3 is constituted by attaching a push button 7 to the upper part of a sponge 6 containing water so that the sponge 6 can be pressed and deformed. The fuel storage portion 2 communicates with a fuel electrode (not shown) of a direct methanol fuel cell through a liquid-permeable sheet 4A covering the lower side.

  In such a fuel cell fuel supply device 1 of this embodiment, when the push button 7 is pressed to reduce (decrease) the sponge 6, the water is stored in the fuel storage portion via the liquid permeable sheet 4. 2 is supplied. When this water comes into contact with the methanol clathrate compound 5, a fuel for a fuel cell made of an aqueous methanol solution is produced. The aqueous methanol solution that is the fuel solution for the fuel cell flows out of the lower liquid-permeable sheet 4A due to the supply pressure of water from the sponge 6 and is supplied to the fuel electrode of the fuel cell.

Next, a second embodiment of the present invention will be described with reference to FIGS.
3 and FIG. 4, the fuel supply device 11 for a fuel cell includes a fuel storage portion 12 and a push button 13 as the flow means 3 provided in connection with the upper surface of the storage portion 12. The fuel container 12 has an upper surface covered with a flexible sheet 14, while a lower surface is a liquid permeable sheet 15 and is filled with a fuel capsule 16 in which a methanol aqueous solution as a liquid fuel component is enclosed. Has been. Thus, in this embodiment, the liquid fuel component is fixed by enclosing the methanol aqueous solution in the fuel capsule 16 so that it can be safely carried. The fuel storage portion 12 communicates with a fuel electrode (not shown) of a direct methanol fuel cell through a liquid-permeable sheet 15 covering the lower side.

  In the fuel cell fuel supply device 11 of this embodiment, when the push button 13 is pressed, the flexible sheet 14 is bent without breaking, and the push button 13 is pushed into the fuel storage portion 12. The volume of the fuel storage portion 12 is reduced, the fuel capsule 16 is pressure-lossed, and the methanol aqueous solution leaks. The methanol aqueous solution that is the fuel solution for the fuel cell is pressed by the pressure of the push button 13 and the lower liquid permeable sheet 15. And is supplied to the fuel electrode of the fuel cell.

Further, a third embodiment of the present invention will be described with reference to FIGS.
5 and 6, the fuel supply device 21 for the fuel cell includes a fuel storage portion 22 and a push button 23 as the flow means 3 provided to be connected to the upper surface of the storage portion 22. The fuel container 22 has an upper surface covered with a flexible sheet 24, while a lower surface is a liquid permeable sheet 25, a water capsule 26 in which water is enclosed, a methanol clathrate compound 27, Is filled. As described above, in this embodiment, methanol, which is a liquid fuel component, is used as an inclusion compound, and water is sealed in a capsule so that the liquid fuel component is fixed and can be safely carried. The fuel storage portion 22 communicates with a fuel electrode (not shown) of a direct methanol fuel cell via a liquid-permeable sheet 25 covering the lower side.

  In such a fuel cell fuel supply device 21 of the present embodiment, when the push button 23 is pressed, the flexible sheet 24 is bent without breaking, and the push button 23 is pushed into the fuel accommodating portion 22. When the volume of the fuel storage unit 22 is reduced, the water capsule 26 is compressed and water leaks, and the water comes into contact with the methanol clathrate compound 27, thereby producing a fuel solution for a fuel cell made of an aqueous methanol solution. The aqueous methanol solution that is the fuel solution for the fuel cell flows out from the lower liquid-permeable sheet 25 due to the pressure caused by the push button 23 and is supplied to the fuel electrode of the fuel cell.

  In the second and third embodiments described above, a liquid fuel absorber such as a sponge lump or the like is mixed in the fuel storage portions 12 and 22 so that the push buttons 13 and 23 are stopped when power supply by the fuel cell is stopped. When the pressure due to is released, the liquid fuel absorber such as a sponge lump expands to absorb excess liquid in the fuel storage portions 12 and 22. Note that the liquid fuel absorber is preferably one that does not absorb liquid when pressed, but can absorb liquid when the pressure is reduced.For example, the liquid absorbency changes by controlling the pressure. The polymer absorber may be used, or the temperature may be controlled according to the pressure using a thermosensitive gel.

  In the first to third embodiments as described above, examples of the fuel for fuel cell (or liquid fuel component) include alcohols, ethers, hydrocarbons, acetals, and the like. Any material can be used as long as it can be used as fuel for the fuel cell, and the present invention is not limited to these. Specifically, alcohols such as hydrogen, methanol, ethanol, n-propanol, isopropanol, and ethylene glycol; ethers such as dimethyl ether, methyl ethyl ether, and diethyl ether; hydrocarbons such as propane and butane; dimethoxymethane, trimethoxy Although acetals, such as methane, etc. are mentioned, it is not limited to these, Moreover, these may be used individually by 1 type and may be used in mixture of 2 or more types.

  The fuel cell is preferably a solid polymer fuel cell. Among them, a direct methanol fuel cell is suitable, but is not limited thereto.

  As the fuel for the fuel cell, a fuel composition for a fuel cell solidified or gelled as a molecular compound or polymer of the fuel for the fuel cell can be used.

  The molecular compound is a compound in which two or more kinds of compounds that can exist stably alone are bonded by a relatively weak interaction other than a covalent bond, such as a hydrogen bond or van der Waals force. And hydrates, solvates, addition compounds, inclusion compounds and the like. Such a molecular compound can be formed by a contact reaction between the compound forming the molecular compound and the fuel for the fuel cell, and the fuel for the fuel cell can be changed into a solid compound, which is relatively light and stable. The fuel for the fuel cell can be stored.

  Examples of the molecular compound include an inclusion compound in which a fuel for a fuel cell is included by a contact reaction between a host compound and a fuel for a fuel cell.

  Among molecular compounds, host compounds that form an inclusion compound that includes a fuel for a fuel cell are known, and organic compounds, inorganic compounds, and organic / inorganic composite compounds are known. Molecular systems, multimolecular systems, polymer hosts, and the like are known.

  Examples of the monomolecular host include cyclodextrins, crown ethers, cryptands, cyclophanes, azacyclophanes, calixarenes, cyclotriveratrylenes, spherands, and cyclic oligopeptides. Multimolecular hosts include ureas, thioureas, deoxycholic acids, cholic acids, perhydrotriphenylenes, tri-o-thymotides, bianthryls, spirobifluorenes, cyclophosphazenes, monoalcohols Diols, hydroxybenzophenones, acetylene alcohols, phenols, bisphenols, trisphenols, tetrakisphenols, polyphenols, naphthols, bisnaphthols, diphenylmethanols, carboxylic acid amides, thioamides, bixanthene , Carboxylic acids, imidazoles, hydroquinones and the like. In addition, as a polymer host, celluloses, starches, chitins, chitosans, polyvinyl alcohols, polyethylene glycol arm type polymers having 1,1,2,2, -tetrakisphenylethane as a core, α, Examples include polyethylene glycol arm type polymers having α, α ′, α′-tetrakisphenylxylene as a core. In addition, organophosphorus compounds, organosilicon compounds, and the like are also included.

  Examples of the inorganic host compound include titanium oxide, graphite, alumina, transition metal dicargogenite, lanthanum fluoride, clay mineral (montmorillonite, etc.), silver salt, silicate, phosphate, zeolite, silica, porous glass, and the like. It is done.

  Furthermore, some organometallic compounds exhibit properties as host compounds. For example, organoaluminum compounds, organotitanium compounds, organoboron compounds, organozinc compounds, organoindium compounds, organogallium compounds, organotellurium compounds, organotins. Examples thereof include compounds, organic zirconium compounds, and organic magnesium compounds. Moreover, it is possible to use a metal salt of an organic carboxylic acid, an organic metal complex, or the like, but it is not particularly limited as long as it is an organic metal compound.

  Of these host compounds, multimolecular hosts whose inclusion ability is less affected by the molecular size of the guest compound are more effective.

  Specific examples of the multimolecular host compound include urea, 1,1,6,6-tetraphenylhexa-2,4, -diyne-1,6-diol, 1,1-bis (2,4- Dimethylphenyl) -2-propyn-1-ol, 1,1,4,4, -tetraphenyl-2-butyne-1,4-diol, 1,1,6,6, -tetrakis (2,4,- Dimethylphenyl) -2,4-hexadiyne-1,6-diol, 9,10-diphenyl-9,10-dihydroanthracene-9,10-diol, 9,10-bis (4-methylphenyl) -9,10 -Dihydroanthracene-9,10-diol, 1,1,2,2-tetraphenylethane 1,2-diol, 4-methoxyphenol, 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzopheno 2,2 ′, 4,4′-tetrahydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-sulfonylbisphenol, 2,2′-methylenebis (4-methyl-6-t -Butylphenol), 4,4'-ethylidenebisphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-) Butylphenyl) butane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethylene, 1,1,2,2-tetrakis (3 -Methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, α, α, α ', α '-Tetrakis (4-hydroxyphenyl) -p-xylene, 3,6,3', 6'-tetramethoxy-9,9'-bi-9H-xanthene, 3,6,3'6'-totraacetoxy- 9,9′-bi-9H-xanthene, gallic acid, methyl gallate, catechin, bis-β-naphthol, α, α, α ′, α′-tetraphenyl 1,1′-biphenyl-2,2′- Dimethanol, diphenic acid bis (dicyclohexylamide), fumarate bis (dicyclohexylamide), cholic acid, deoxycholic acid, 1,1,2,2-tetrakis (4-carboxyphenyl) ethane, 1,1,2,2 -Tetrakis (3-carboxyphenyl) ethane, acetylenedicarboxylic acid, 2,4,5-triphenylimidazole, 1,2,4,5-tetraphenylimidazole, 2- Phenylphenanthro [9,10-d] imidazole, 2- (o-cyanophenyl) phenanthro [9,10-d] imidazole, 2- (m-cyanophenyl) phenanthro [9,10-d] imidazole, 2 -(P-cyanophenyl) phenanthro [9,10-d] imidazole, hydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis (2,4-dimethylphenyl) Although hydroquinone etc. are mentioned, a phenol type host compound like 1, 1-bis (4-hydroxyphenyl) cyclohexane is advantageous at the point which is easy to use industrially.

  These host compounds may be used individually by 1 type, and may use 2 or more types together. These host compounds may be any shape compounds as long as they form a solid clathrate compound with the fuel for the fuel cell.

  The organic host compound described above can also be used as an organic / inorganic composite material supported on an inorganic porous material. In this case, examples of the porous material supporting the organic host compound include silica, zeolites, activated carbons, intercalation compounds such as clay minerals and montmorillonites, but are not limited thereto. Absent.

  Such an organic / inorganic composite material is manufactured, for example, by dissolving the organic host compound in a solvent that can dissolve the organic host compound, impregnating the solution in an inorganic porous material, and drying and drying under reduced pressure. Can do. Although there is no restriction | limiting in particular as the load of the organic host compound with respect to an inorganic porous material, Usually, it is about 10-80 mass% with respect to an inorganic porous material.

  As a method of synthesizing a fuel cell fuel clathrate compound using a host compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane described above, for example, a fuel cell fuel and a host compound are directly contacted and mixed. And a method in which the host compound is dissolved in a fuel for a fuel cell by heating, etc., and recrystallized. When the fuel cell fuel is a gas or liquid, the fuel cell fuel clathrate compound can be obtained by contacting the fuel with the host compound in a pressurized state.

  The temperature at which the fuel for the fuel cell is brought into contact with the host compound is not particularly limited, but is preferably from room temperature to about 100 ° C. The time for contacting the fuel cell fuel with the host compound is not particularly limited, but is preferably about 0.01 to 24 hours from the viewpoint of work efficiency.

  The fuel for the fuel cell to be brought into contact with the host compound is preferably a high-purity fuel. However, when a host compound having the selective inclusion ability of the fuel for the fuel cell is used, the fuel for the fuel cell and other components are used. And a mixed liquid.

  The clathrate compound thus obtained varies depending on the type of the host compound used, the contact conditions with the fuel for the fuel cell, etc. An inclusion compound containing 10 moles.

  The clathrate compound thus obtained can stably store fuel for fuel cells over a long period of time in a normal temperature / normal pressure environment. In addition, the inclusion compound is lightweight, excellent in handleability, and solid, so it can be easily stored in a glass, metal, plastic or other container, and the problem of liquid leakage is also eliminated. . In addition, since the liquid fuel is usually solidified by inclusion, the property as a deleterious substance or a dangerous substance can be avoided. Furthermore, the chemical reactivity of the fuel cell fuel can be reduced, and for example, the corrosiveness to metals can be alleviated.

  The fuel composition contains 20 to 100% by mass of a structural unit having a carboxyl group and / or a sulfonic acid group in the molecule based on the polymer (1), and the carboxyl group and / or the sulfonic acid group. A fuel composition for a fuel cell comprising a cross-linked product (A) of the polymer (1) in which 30 to 100 mol% of protons are substituted with an onium cation and a fuel for a fuel cell can also be used. In order to absorb and gel a fuel for a fuel cell (hereinafter simply referred to as fuel), it contains a predetermined amount of a structural unit having a carboxyl group and / or sulfonic acid group in the molecule, and the carboxyl group and / or sulfonic acid group The cross-linked product (A) of the polymer (1) obtained by substituting a certain amount of proton with a predetermined amount of onium cation is used.

  As the structural unit (a) having a carboxyl group and / or a sulfonic acid group constituting the crosslinked body (A), a monomer having a carboxyl group [for example, (meth) acrylic acid, ethacrylic acid, crotonic acid, sorbic acid, Maleic acid, itaconic acid, fumaric acid, cinnamic acid, and their anhydrides]; monomers having sulfonic acid groups [for example, aliphatic vinyl sulfonic acids [vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene] Sulfonic acid etc.], (meth) acrylate type sulfonic acid [sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate etc.) and (meth) acrylamide type sulfonic acid [eg acrylamide-2-methylpropane sulfonic acid etc.] etc. And one or more of these are included in the polymer (1). It is possible to the unit. Preferably, it is a structural unit having a C 3-30 carboxyl group and / or a sulfonic acid group.

  Further, as a method for obtaining a polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group in the molecule, in addition to a method of polymerizing a predetermined amount of the monomer (a), for example, A monomer that can be easily changed to a carboxyl group or a sulfonic acid group, such as an esterified product or an amidated product of the carboxyl group or sulfonic acid group-containing monomer, is polymerized, and a predetermined amount of the carboxyl group is obtained using a method such as hydrolysis. And a method of introducing a structural unit of a sulfonic acid group into the molecule, and the polymer (1) includes a carboxyl group typified by carboxymethyl cellulose, a sulfonic acid group-containing polysaccharide polymer, and the polymer. Examples include graft copolymers of saccharide polymers and other monomers, but the final component of carboxyl group and / or sulfonic acid group The not particularly limited as long as a predetermined amount containing polymer is obtained.

  Content in the polymer (1) of the structural unit which has a carboxyl group and / or a sulfonic acid group is 20-100 mass% normally, Preferably it is 40-100 mass%, More preferably, it is 60-100 mass%. When the content is less than 20%, even if the proton of a carboxyl group or sulfonic acid group is replaced with an onium cation described later, the amount of absorption with respect to the target liquid fuel decreases, or the liquid fuel cannot be gelled with a small amount There is.

  Examples of the copolymerizable monomer (b) that forms a structural unit other than the structural unit having a carboxyl group and / or a sulfonic acid group include (meth) alkyl acrylate (C 1-30) esters [(meta ) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethyl hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) Stearyl acrylate, phenyl (meth) acrylate, octylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.]; (meth) acrylic acid oxyalkyl (C1-4) [hydroxy (meth) acrylate Ethyl, hydroxypropyl (meth) acrylate, mono (meth) acrylate (polyethylene) Recall) ester (PEG number average molecular weight: 100 to 4000), (meth) acrylic acid mono (polypropylene glycol) ester (PPG number average molecular weight: 100 to 4000), (meth) acrylic acid monomethoxypolyethylene glycol (PEG number average molecular weight) : 100-4000), (meth) acrylic acid monomethoxypropylene glycol (PPG number average molecular weight: 100-4000), etc.]; (meth) acrylamides [(meth) acrylamide, (di) methyl (meth) acrylamide, (di ) Ethyl (meth) acrylamide, (di) propyl (meth) acrylamide, etc.]; allyl ethers [methyl allyl ether, ethyl allyl ether, propyl allyl ether, glycerol monoallyl ether, trimethylolpropane triallyl Ether, pentaerythritol monoallyl ether, etc.]; α-olefins having 4 to 20 carbon atoms [isobutylene, 1-hexene, 1-octene, isooctene, 1-nonene, 1-decene, 1-dodecene, etc.]; ~ 20 aromatic vinyl compounds [styrene, t-butylstyrene, octylstyrene, etc.]; other vinyl compounds [N-vinylacetamide, vinyl caproate, vinyl laurate, vinyl stearate, etc.]; amino group-containing monomers [ Dialkyl (carbon number of alkyl: 1 to 5) aminoethyl (meth) acrylate, meth (acryloyl) oxyethyltrialkyl (alkyl carbon number: 1 to 5) ammonium chloride, bromide, sulfate, etc.]; carboxyl group, sulfonic acid Alkali metal salt of a monomer having a group; 1 Tertiary amine salts; alkanolamine salts and the like. One or more of these monomers (b) may be copolymerized with the above (a) within a predetermined amount range (less than 80% of the polymer structural unit) as necessary.

  Among the monomers (b), (meth) acrylic acid alkyl esters, oxyalkyl (meth) acrylates, allyl ethers, α-olefins from the viewpoints of polymerizability of the monomer and stability of the produced polymer. Aromatic vinyl compounds are preferred.

  It is better to select the monomer (b) whose difference between the SP value of the solvent and the monomer (b) is 5 or less according to the SP value (solubility parameter) of the solvent to be absorbed or gelled by the liquid fuel. It is preferable because the absorption amount and gelling power are easily increased, and it is more preferable to select a solvent having an SP value of the target solvent and an SP value of the monomer (b) of 3 or less.

  It is desirable to substitute 30 to 100 mol% of protons of the carboxyl group and / or sulfonic acid group with an onium cation. As the onium cation, one kind selected from the group consisting of a quaternary ammonium cation (I), a tertiary sulfonium cation (II), a quaternary phosphonium cation (III), and a tertiary oxonium cation (IV) or 2 or more types.

Examples of the quaternary ammonium cation (I) include the following (I-1) to (I-11).
(I-1) C4-C30 or higher aliphatic quaternary ammonium having an alkyl and / or alkenyl group; tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethyl Propyl ammonium, tetrapropyl ammonium, butyl trimethyl ammonium, tetrabutyl ammonium and the like.

  (I-2) Aromatic quaternary ammonium having 6 to 30 or more carbon atoms; trimethylphenylammonium, dimethylethylphenylammonium, triethylphenylammonium and the like.

  (I-3) C3-C30 or more alicyclic quaternary ammonium; N, N-dimethylpyrrinium, N-ethyl-N-methylpyrrolidinium, N, N-dimethylmorpholinium N, N-diethylmorpholinium, N, N-dimethylpiperidinium, N, N-diethylpiperidinium and the like.

  (I-4) imidazolinium having 3 to 30 or more carbon atoms; 1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl 2-ethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1,2-dimethyl-3-ethylimidazolinium, 1-ethyl-3-methylimidazolinium, 1,2 , 3,4-tetraethylimidazolinium, 1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 2-cyanomethyl-1,3-dimethylimidazolinium, 4 -Acetyl-1,2,3-trimethylimidazolinium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolinium, 4-formyl-1,2, - trimethyl imidazolinium, 3-hydroxyethyl-1,2,3-trimethyl imidazolinium, 1,2 3-hydroxyethyl dimethyl imidazolinium like.

  (I-5) imidazolium having 3 to 30 or more carbon atoms; 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1,2,3 , 4-tetramethylimidazolium, 1,2-dimethyl-3-ethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-ethylimidazolium, 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 4-cyano-1,2,3-trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 4-methoxy- , 2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazolium, N, N'-dimethylbenzimidazolium, N, N'- Diethyl benzimidazolium, N-methyl-N′-ethyl benzimidazolium and the like.

  (I-6) Tetrahydropyrimidinium having 4 to 30 or more carbon atoms; 1,3-dimethyltetrahydropyrimidinium, 1,2,3-trimethyltetrahydropyrimidinium, 1,2,3,4-tetra Methyltetrahydropyrimidinium, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium, 5-methyl-1,5-diazabicyclo [4,3,0] -5-nonenium, 3- Cyanomethyl-1,2-dimethyltetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyltetrahydropyrimidinium, 4-methylcarboxymethyl-1,2,3-trimethyl-tetrahydropyrimidinium, 3-methoxymethyl -1,2-dimethyltetrahydropyrimidinium, 4-hydroxymethyl-1,3-dimethyltetra Mud pyrimidinium like.

  (I-7) Dihydropyrimidinium having 4 to 30 or more carbon atoms; 1,3-dimethyl-2,4- or -2,6-dihydropyrimidinium [these are 1,3-dimethyl-2, This is expressed as 4 (6) -dihydropyrimidinium, and the same expression is used hereinafter. 1,2,3-trimethyl-2,4 (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-2,4 (6) -dihydropyrimidinium, 1,2,3 , 5-tetramethyl-2,4 (6) -dihydropymidinium, 8-methyl-1,8-diazacyclo [5,4,0] -7,9 (10) -undecandienium, 2-cyanomethyl- 1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-2,4 (6) -dihydropyrimidinium, 4-methylcarboxymethyl-1,2 , 3-trimethyl-2,4 (6) -dihydropyrimidinium, 4-formyl-1,2,3-trimethyl-2,4 (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2- Dimethyl-2,4 (6) -dihydropi Mijiniumu like.

  (I-8) Guanidium having an imidazolinium skeleton having 3 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazole Linium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, 2-dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-dimethylimidazolinium, 2- Diethylamino-1,3-diethylimidazolinium, 1,5,6,7-tetrahydro1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl- 2H-pyrimido [1,2a] imidazolinium, 2-dimethylamino-3-methylcarboxymethyl-1-methylimidazoli , 2-dimethylamino-3-methoxymethyl-1-methylimidazolinium, 2-dimethylamino-3-hydroxyethyl-1-methylimidazolinium, 2-dimethylamino-4-hydroxymethyl-1,3- Dimethylimidazolinium etc.

  (I-9) Guanidium having an imidazolium skeleton having 3 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-diethylamino-1,3,4-triethylimidazolium, 2-dimethylamino-1,3-dimethylimidazolium, 1,5,6,7 -Tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido- [1,2a] imidazolium, 2-dimethylamino-3 -Cyanomethyl-1-methylimidazolium, 2-dimethylamino-4-methylcarboxymethyl-1,3-dimethyli Dazolium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolium, 2-dimethylamino-3-formylmethyl-1-methylimidazolium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazole Lium etc.

  (I-10) Guanidium having a tetrahydropyrimidinium skeleton having 4 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethyltetrahydropyrimidinium, 2-diethylamino-1,3,4- Trimethyltetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyltetrahydropyrimidinium, 2-diethylamino-1,3-dimethyltetrahydropyrimidinium, 1,3,4,6,7,8-hexahydro-1 , 2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino- 3-cyanomethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino-4-acetyl-1 3-dimethyltetrahydropyrimidinium 2-dimethylamino-4-methylcarboxymethyl-1,3-dimethyltetrahydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino -3-hydroxyethyl-1-methyltetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyltetrahydropyrimidinium, and the like.

  (I-11) Guanidium having a dihydropyrimidinium skeleton having 4 to 30 or more carbon atoms; 2-dimethylamino-1,3,4-trimethyl-2,4 (6) -dihydropyrimidinium, 2- Diethylamino-1,3,4-trimethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3,4-triethyl-2,4 (6) -dihydropyrimidinium, 2-diethylamino- 1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-2,4 (6) -dihydropyrimidinium, 1,6,7,8 -Tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethyl Ruamino-4-cyano-1,3-dimethyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-methylcarboxymethyl-1-methyl-2,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyl-2,4 (6) -dihydro Pyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-2,4 (6) -dihydropyrimidinium, and the like.

Examples of the tertiary sulfonium cation (II) include the following (II-1) to (II-3).
(II-1) Aliphatic tertiary sulfonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; trimethylsulfonium, triethylsulfonium, ethyldimethylsulfonium, diethylmethylsulfonium and the like.

  (II-2) Aromatic tertiary sulfonium having 6 to 30 or more carbon atoms; phenyldimethylsulfonium, phenylethylmethylsulfonium, phenylmethylbenzylsulfonium and the like.

  (II-3) Alicyclic tertiary sulfonium having 3 to 30 or more carbon atoms; methylthiolanium, phenylthiolanium, methylthianium and the like.

Examples of the quaternary phosphonium cation (III) include the following (III-1) to (III-3).
(III-1) Aliphatic quaternary phosphonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, methyltriethylphosphonium, methyl Tripropylphosphonium, methyltributylphosphonium, dimethyldiethylphosphonium, dimethyldibutylphosphonium, trimethylethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, etc.

  (III-2) Aromatic quaternary phosphonium having 6 to 30 or more carbon atoms; triphenylmethylphosphonium, diphenyldimethylphosphonium, triphenylbenzylphosphonium and the like.

  (III-3) alicyclic quaternary phosphonium having 3 to 30 or more carbon atoms; 1,1-dimethylphosphoranium, 1-methyl-1-ethylphosphonium, 1,1-diethylphosphonium, 1,1-diethyl phosphorinanium, 1,1-pentaethylene phosphorinanium, and the like.

Examples of the tertiary oxonium cation (IV) include the following (IV-1) to (IV-3).
(IV-1) Aliphatic tertiary oxonium having an alkyl and / or alkenyl group having 1 to 30 or more carbon atoms; trimethyloxonium, triethyloxonium, ethyldimethyloxonium, diethylmethyloxonium and the like.

  (IV-2) Aromatic tertiary oxonium having 6 to 30 or more carbon atoms; phenyldimethyloxonium, phenylethylmethyloxonium, phenylmethylbenzyloxonium and the like.

  (IV-3) An alicyclic tertiary oxonium having 3 to 30 or more carbon atoms; methyl oxolanium, phenyl oxolanium, methyl oxonium and the like.

  Among these, a preferable onium cation is (I), more preferable are (I-1), (I-4) and (I-5), and particularly preferable are (I-4) and (I I-5). These onium cations may be used alone or in combination of two or more.

  Examples of the method of introducing the onium cation into the polymer include a method of substituting the proton of the carboxyl group and / or sulfonic acid group of the polymer with the onium cation. As a method for substituting protons with the onium cation, any method can be used as long as it is a method capable of substituting a predetermined amount of onium cation. For example, a hydroxide salt of the onium cation (for example, tetraethylammonium hydroxide). Etc.) and a monomethyl carbonate salt (for example, 1,2,3,4-trimethylimidazolinium monomethyl carbonate, etc.) are added to a polymer containing a carboxyl group and / or a sulfonic acid group, and if necessary, dehydration, It can be easily replaced by decarboxylation, demethanol, or the like. Moreover, you may substitute similarly in the stage of a monomer.

  Regarding the stage of substitution with an onium cation, for example, a method of polymerizing after the monomer containing a carboxyl group and / or sulfonic acid group is substituted with an onium cation, or a polymer having a carboxyl group and / or a sulfonic acid group is prepared. Then, a method of substituting the proton of the acid with an onium cation can be mentioned, but it may be carried out at any stage as long as the proton of the carboxyl group and / or sulfonic acid group of the final polymer is substituted.

  The degree of substitution of the proton of the carboxyl group and / or sulfonic acid group with the onium cation (substitution degree) is 30 to 100 mol%, preferably 50 to 100 mol%, more preferably 70 to 100 mol%. When the degree of substitution by the onium cation is less than 30 mol%, the dissociation of the carboxyl group, sulfonic acid group and onium cation of the polymer (1) is too low, and the swelling power and gelling power may be low.

  In the present invention, the polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group and having the carboxyl group and / or the sulfonic acid group substituted with a predetermined amount of an onium cation, Specifically, it is crosslinked at any stage to obtain a crosslinked product. The crosslinking method may be a known method, and examples thereof include the following methods [1] to [5].

[1] Crosslinking with a copolymerizable crosslinking agent Copolymerizable with the carboxyl group and / or sulfonic acid group-containing monomer, an onium cation-substituted product of the monomer, and another monomer (b) to be copolymerized if necessary, or within the molecule Copolymerizable crosslinking agent having two or more double bonds [for example, polyvalent vinyl type crosslinking agent such as divinylbenzene, (meth) acrylamide type crosslinking agent such as N, N′-methylenebisacrylamide, pentaerythritol triallyl ether For example, a polyvalent allyl ether type cross-linking agent such as trimethylolpropane triacrylate and the like.

[2] Crosslinking with a reactive crosslinking agent Reactivity having two or more functional groups in the molecule that can react with a carboxyl group and / or a sulfonic acid group or an onium cation substitution product thereof, and a functional group of a monomer to be copolymerized if necessary Crosslinker [for example, polyvalent isocyanate type crosslinker such as 4,4′-diphenylmethane diisocyanate, polyvalent epoxy type crosslinker such as polyglycerol polyglycidyl ether, polyhydric alcohol type crosslinker such as glycerin, hexamethylenetetramine and polyethylene And a polyvalent amine such as imine, an imine type cross-linking agent, a haloepoxy type cross-linking agent such as epichlorohydrin, and a polyvalent metal salt type cross-linking agent such as aluminum sulfate.

[3] Crosslinking with a polymerization-reactive crosslinker The carboxyl group and / or sulfonic acid group-containing monomer, an onium cation-substituted product of the monomer, and, if necessary, copolymerizable with other monomer (b) or within the molecule Polymerization-reactive crosslinking agent having a double bond and having a functional group in the molecule that can react with a carboxyl group and / or a sulfonic acid group or an onium cation substitution product thereof, and a functional group of a monomer to be copolymerized if necessary [ For example, glycidyl (meth) acrylate type crosslinking agents such as glycidyl methacrylate, and allyl epoxy type crosslinking agents such as allyl glycidyl ether].

[4] Crosslinking by radiation irradiation A method of crosslinking the polymer (1) by irradiating the polymer (1) with radiation such as ultraviolet rays, electron beams, γ rays, etc., and the monomer with ultraviolet rays, electron beams, γ rays, etc. A method of performing polymerization and crosslinking at the same time by irradiation.

[5] Crosslinking by heating The polymer (1) is heated to 100 ° C. or more, and thermal crosslinking is performed between the molecules of the polymer (1) (for example, between carbons due to generation of radicals by heating or between functional groups). Cross-linking).

  Among these crosslinking methods, preferred ones vary depending on the use and form of the final product, but when considered comprehensively, [1] crosslinking with a copolymerizable crosslinking agent, [2] crosslinking with a reactive crosslinking agent, and [4] Cross-linking by radiation irradiation.

  Among the copolymerizable crosslinking agents, preferred are polyvalent (meth) acrylamide type crosslinking agents, allyl ether type crosslinking agents, and polyvalent (meth) acrylic acid ester type crosslinking agents, and more preferred are allyl ethers. It is a mold cross-linking agent.

  Among the reactive crosslinking agents, preferred are a polyvalent isocyanate type crosslinking agent and a polyvalent epoxy type crosslinking agent, and more preferred are a polyvalent isocyanate type crosslinking agent having three or more functional groups in the molecule or It is a polyvalent epoxy type cross-linking agent.

  The degree of crosslinking can be appropriately selected depending on the purpose of use, but when a copolymerizable crosslinking agent is used, it is preferably 0.001 to 10% by mass, and 0.01 to 5% by mass with respect to the total monomer mass. Further preferred.

  The amount of addition in the case of using a reactive cross-linking agent varies depending on the shape of the cross-linked product (A), but is preferably 0.001 to 10% by mass. In the case of producing an integrated gel containing fuel, 0.01 to 50% by mass is preferable.

  In the present invention, the polymerization method of the carboxyl group and / or sulfonic acid group-containing monomer, the onium cation-substituted product of the monomer, and other monomer (b) copolymerized as necessary may be a known method. Examples thereof include a solution polymerization method in a solvent in which a monomer and a polymer to be generated are dissolved, a bulk polymerization method in which polymerization is performed without using a solvent, and an emulsion polymerization method. Among these, the solution polymerization method is preferable.

  The organic solvent by solution polymerization can be selected as appropriate depending on the solubility of the monomer and polymer used, for example, alcohols such as methanol and ethanol; carbonates such as ethylene carbonate, propylene carbonate and dimethyl carbonate; γ-butyrolactone, etc. Lactones; lactones such as ε-caprolactam; ketones such as acetone and methyl ethyl ketone; carboxylic acid esters such as ethyl acetate; ethers such as tetrahydrofuran and dimethoxyethane; aromatic hydrocarbons such as toluene and xylene; and water Etc. These solvents may be used alone or in combination of two or more.

  The polymerization concentration in the solution polymerization is not particularly limited and may vary depending on the intended use, but is preferably 1 to 80% by mass, more preferably 5 to 60% by mass.

  The polymerization initiator may be a normal one, such as an azo initiator [azobisisobutyronitrile, azobiscyanovaleric acid, azobis (2,4-dimethylvaleronitrile), azobis (2-amidinopropane) dihydrochloride, azobis { 2-methyl-N- (2-hydroxyethyl) propionamide} and the like], peroxide initiators [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, succinic peroxide, di ( 2-ethoxyethyl) peroxydicarbonate, hydrogen peroxide, etc.] and redox initiators [a combination of the above peroxide-based initiators and a reducing agent (ascorbic acid or persulfate), etc.].

  Examples of other polymerization methods include a method of adding a photosensitizing initiator [benzophenone or the like] and irradiating with ultraviolet rays or the like, a method of irradiating with radiation such as γ rays or electron beams, and the like.

  The amount of initiator added when a polymerization initiator is used is not particularly limited, but is preferably 0.0001 to 5% by mass, more preferably 0.001 to 2% by mass, based on the total mass of the monomers used. preferable.

  The polymerization temperature also varies depending on the target molecular weight, the decomposition temperature of the initiator, the boiling point of the solvent used, etc., but is preferably -20 to 200 ° C, more preferably 0 to 100 ° C.

  When making a crosslinked body into a particulate form, the particle diameter is 0.1-5000 micrometers in a volume average particle diameter, More preferably, it is 50-2000 micrometers. Further, the portion less than 0.1 μm is 10% by mass or less of the whole, and the portion exceeding 5000 μm is preferably 10% by mass or less, more preferably 5% by mass or less.

  The particle size was measured in the Perry's Chemical Engineers Handbook 6th Edition (McGlow Hill Book Company, 1984, p.21) using a low tap test sieve shaker and a JIS Z8801-2000 standard sieve. (Hereinafter, the particle diameter is measured by this method.)

The method for obtaining the particulate form is not particularly limited as long as it finally becomes particulate, and examples thereof include the following methods (i) to (iv).
(I) If necessary, using a solvent, adding the copolymerizable crosslinking agent to prepare a crosslinked body (A) of the polymer (1) by copolymerization, and if necessary, removing the solvent by a method such as drying. A method of pulverizing into particles using a known pulverization method.

  (Ii) If necessary, polymerize using a solvent to prepare the polymer (1), and then crosslink the polymer (1) by means of the reactive crosslinking agent or radiation irradiation, and then dry if necessary. A method in which the solvent is distilled off by a method such as pulverization using a known pulverization method to form particles.

  (Iii) The carboxyl group and / or sulfonic acid group-containing monomer and, if necessary, another monomer (b) in the presence of the copolymerizable crosslinking agent, if necessary, are copolymerized using a solvent to be crosslinked and polymerized. Then, after adding the onium cation compound and replacing the proton of the acidic group with a predetermined amount of onium cation, if necessary, the solvent is distilled off by a method such as drying, and pulverization is performed using a known pulverization method. how to.

  (Iv) An uncrosslinked polymer obtained by copolymerizing the carboxyl group and / or sulfonic acid group-containing monomer and, if necessary, another monomer (b) in the absence of the copolymerizable crosslinking agent, if necessary, using a solvent. Then, by adding the onium cation compound and the reactive crosslinking agent or by irradiation with radiation, the polymer is crosslinked at the same time as replacing the proton of the acidic group, and if necessary, the solvent is distilled off by a method such as drying, A method in which particles are pulverized using a known pulverization method.

  In the process of making the cross-linked product (A) of these fuel cell fuel storages (hereinafter referred to as fuel storages) into a particulate form, the drying performed as necessary may be performed by a known drying method. For example, ventilation drying (circulation) And air drying (such as a band-type dryer), vacuum drying (such as a vacuum dryer), and contact drying (such as a drum dryer).

  The drying temperature for drying is not particularly limited as long as the polymer or the like does not deteriorate or excessively cross-linked, but is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The pulverization method when the shape is in the form of particles may be a known method, for example, impact pulverization (pin mill, cutter mill, ball mill type pulverizer, high-speed rotary pulverizer such as ACM pulverizer, etc.) Etc.), and a method such as freeze pulverization.

  In this way, a particulate crosslinked body (A) is obtained. In the present invention, the cross-linked product (A) in the fuel storage of the present invention that has been particulated in this way has the ability to absorb fuel.

  The fuel composition accommodated in the fuel supply device for a fuel cell of the present invention can be processed into various forms, and the form of the fuel composition is not particularly limited, but as a preferred form, it is in the form of particles, sheets, and integral gelation. Can be mentioned.

  Hereinafter, a method for creating a preferable form will be described. However, a method for creating the preferred form, a preferable method, and the like differ slightly depending on the form, and each will be described.

  The particulate fuel storage product may be one in which the particulate crosslinked body (A) has absorbed the fuel, or may be particulate after the fuel has been absorbed. The method for forming particles may be the same as the method for producing the crosslinked body (A). The same volume average particle diameter as that of the crosslinked body (A) is preferable.

  The particulate fuel composition is capable of absorbing fuel. The amount of the crosslinked product (A) absorbed in the fuel storage of the present invention varies depending on the type of the target fuel, the polymer composition, the gel strength, etc., and the crosslinked product (A) is used as the fuel storage. When using, it is preferable to design the absorption amount with respect to methanol to 10-1000 g / g, and it is more preferable to design to 50-900 g / g. If the absorption amount is 10 g / g or more, the liquid retention amount is significantly larger than that of the conventional nonionic absorbent, and if it is 1000 g / g or less, the gel strength of the fuel stock holding liquid fuel is too weak. There is no problem.

  Next, the case where the fuel composition is in the form of a sheet will be described. Examples of the method for forming a sheet include the following methods (v) to (vii).

  (V) A method in which the particulate crosslinked product (A) is sandwiched between non-woven fabrics or papers to form a sandwich sheet and absorb fuel.

  (Vi) after impregnating and / or applying a non-crosslinked body of the polymer (1) to a substrate composed of one or more of nonwoven fabric, woven fabric, paper, and film, followed by crosslinking with the crosslinking agent, The polymer (1) is cross-linked by using one or two or more cross-linking means selected from the group consisting of cross-linking by radiation irradiation and cross-linking by heating. To absorb.

  (Vii) Carboxyl group and / or sulfonic acid group-containing monomer in which 30 to 100 mol% of protons are substituted with the onium cation, and 0 to 80 mass% of other copolymerizable monomers, and the crosslinking After impregnating and / or applying a mixed solution composed of an agent to a substrate composed of one or more of nonwoven fabric, woven fabric, paper, and film, the substrate is then subjected to polymerization initiator and / or radiation, etc. A method of polymerizing using one or two or more crosslinking means selected from the group consisting of crosslinking by irradiation and crosslinking by heating, and if necessary, forming a sheet by distilling off the solvent, and then absorbing the fuel.

Among these methods, (vi) or (vii) is preferable from the viewpoint of easy adjustment of the thickness of the prepared sheet (B), the absorption rate of the prepared sheet, and the like. When the shape is a sheet, the thickness of the sheet (B) is preferably 1 to 50000 μm, more preferably 5 to 30000 μm, and particularly preferably 10 to 10000 μm. When the thickness of the sheet is 1 μm or more, the basis weight of the crosslinked body (A) is not too small, and when it is 50000 μm or less, the thickness of the sheet is not too thick. The sheet length and width can be appropriately selected depending on the size to be used, and are not particularly limited. However, the preferred length is 0.01 to 10 m, and the preferred width is 0.1 to 300 cm. The weight per unit area of the crosslinked polymer of the present invention in the sheet (B) is not particularly limited, but taking into account the absorption / retention capacity of the target liquid fuel, the thickness not being too thick, and the like. weight per unit area is preferably 10~3000g / ^{m 2,} more preferably 20~1000g / ^{m 2.}

  A base material such as a nonwoven fabric, a woven fabric, paper, or a film used as necessary to form the sheet may be a well-known material, for example, a synthetic fiber and / or natural fiber having a basis weight of about 10 to 500 g. Nonwoven fabric or woven fabric, paper (quality paper, thin paper, Japanese paper, etc.), a film made of a synthetic resin, and two or more substrates thereof and a composite thereof can be exemplified.

  Among these substrates, preferred are nonwoven fabrics and composites of nonwoven fabrics and plastic films or metal films, and particularly preferred are nonwoven fabrics and composites of nonwoven fabrics and plastic films.

  Although there is no limitation in particular regarding the thickness of these base materials, it is 1-50000 micrometers normally, Preferably it is 10-20000 micrometers. When the thickness is less than 1 μm, it is difficult to impregnate or apply the predetermined amount of the polymer (1). It becomes difficult to use. The coating method or impregnation method of the polymer (1) to the substrate may be a known method, for example, a normal coating or padding method may be applied, and after performing the coating or padding treatment, The solvent used for polymerization, dilution, viscosity adjustment and the like may be distilled off by a method such as drying, if necessary.

The sheet containing the cross-linked product (A) thus prepared absorbs fuel efficiently and is used as a sheet-type fuel storage. The amount of fuel absorbed in the sheet-type fuel storage is not particularly limited as long as the fuel supply time is sufficiently long, but is preferably 0.1 to 500 g-fuel / cm ² -sheet, preferably 1 to 400 g / cm ² . More preferred. When the absorption amount is 0.1 g / cm ² , the liquid fuel can be sufficiently absorbed, and when it is 500 g / cm ² or less, the sheet that has absorbed the liquid fuel does not become too thick.

  The ratio of the crosslinked body (A) / fuel in the integral gelled fuel storage comprising the crosslinked body (A) and fuel is preferably 0.1 to 99/1 to 99.9% by mass, and more preferably. Is 0.5 to 50/50 to 99.5% by mass, particularly preferably 1 to 30/70 to 99% by mass, and most preferably 1 to 20/80 to 99% by mass. When the ratio of the crosslinked body (A) is 0.1% by mass or more, there is no case in which the entire fuel-containing gel having weak gel strength cannot be gelled, while the content is 99% by mass or less. And since there is too much content of this bridge | crosslinking body (A), the addition amount of a fuel required is too low, and the discharge time of a battery is not shortened.

  The same fuel as described above can be used as the fuel used for the integral gelled fuel storage. Examples of a method for producing an integral gelled fuel storage include: (viii) a method of adding a predetermined amount of fuel to the above-described particulate crosslinked body (A) of the present invention; (ix) the crosslinked body (A) However, it is preferable that these fuel-containing gels can create an integrated gel by the methods described in (x) and (xi) below.

  (X) The polymer (1) is dissolved in a fuel, and the polymer (1) is integrated by cross-linking by any cross-linking means of cross-linking by the cross-linking agent, cross-linking by radiation irradiation, or cross-linking by heating. How to make a gel.

  (Xi) 20 to 100% by mass of a carboxyl group and / or sulfonic acid-containing monomer in which 30 to 100 mol% of protons are substituted with the onium cation in the fuel, and 0 to 80% of other copolymerizable monomers as necessary. A method of forming an integrated gel by polymerizing mass% in the presence of the copolymerizable crosslinking agent.

  The form of the gel composed of the crosslinked body and the fuel can be appropriately selected. Examples of the shape include a sheet shape, a block shape, a spherical shape, and a cylindrical shape. Among these, when used as a fuel storage, a preferable shape is a sheet shape, a block shape or a column shape.

  1-50000 micrometers is preferable and, as for the thickness of the gel in setting it as a sheet-like gel, 10-20000 micrometers is still more preferable. What is necessary is just to select suitably about the width | variety and length of a sheet-like gel according to the use purpose, a place, a use, etc.

  There are no particular limitations on the method for producing gels of these shapes. For example, the polymer (1) may be formed on a release paper, a film, a nonwoven fabric, or the like by gelation in a container or cell that matches the shape to be produced. ) Or a mixture of a monomer or the like and a liquid fuel, or a method of forming a sheet-like gel by a method such as lamination or coating.

  The fuel composition may contain other gelling agents (fatty acid soap, dibenzal sorbite, hydroxypropylcellulose, benzylidene sorbitol, carboxyvinyl polymer, polyethylene glycol, polyoxyalkylene, sorbitol, nitrocellulose, methylcellulose, ethylcellulose as necessary. , Acetylbutyl cellulose, polyethylene, polypropylene, polystyrene, ABS resin, AB resin, acrylic resin, acetal resin, polycarbonate, nylon, phenolic resin, phenoxy resin, urea resin, alkyd resin, polyester, epoxy resin, diallyl phthalate resin, polyallomer Etc.), adsorbent (dextrin, dextran, silica gel, silica, alumina, molecular sieve, kaolin, diatomaceous earth, carbon bra Click, activated carbon, etc.), a thickener, a binder, and fuel may be blended with one or more members selected from the group consisting of substances which non-fluidized by chemical transformation. These are not particularly limited as long as they can exhibit their respective functions, and may be solid or liquid. Moreover, you may mix | blend in the arbitrary steps which produce a fuel store.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

[Production Example 1]
By re-dissolving 26.8 g (0.1 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane (BHC) in 50 ml of methanol by heating and recrystallization, BHC: methanol = 1: 1 (molar ratio). A solid methanol clathrate compound having a methanol content of 11% by mass was obtained.

[Production Example 2]
By resolving 39.8 g (0.1 mol) of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (THPE) in 100 ml of methanol by heating and recrystallization, THPE: methanol = 1: 2 ( A solid methanol clathrate compound having a methanol content of 14% by mass was obtained.

[Production Example 3]
360 g (5 mol) of acrylic acid, 1.08 g of pentaerythritol triallyl ether and 1140 g of water were placed in a 2 liter adiabatic polymerization tank. After cooling the temperature of the monomer solution to 0 ° C. and reducing the dissolved oxygen through nitrogen to the solution, 0.36 g of 2,2′-azobis (2-amidinopropane) hydrochloride as a polymerization initiator, 35% peroxidation 3.1 g of hydrogen water and 0.38 g of L-ascorbic acid were added to initiate polymerization. After polymerization, the produced hydrous gel was subdivided using a meat chopper, and then 60% methano of methyl carbonate (molecular weight: 203) of 1,2,3,4-tetramethylimidazolinium cation was added to this gel. When 1353 g (4 moles) of a solution (manufactured by Sanyo Chemical Industries) was added, it was observed that decarboxylation and demethanol occurred. The gel added with the imidazolinium cation was perfused with hot air at 100 ° C. using a band-type dryer (air-permeable dryer, manufactured by Inoue Metals Co., Ltd.), and water used as a solvent and by-product methanol Was distilled off and dried. The obtained dried product was pulverized using a cutter mill to prepare a particulate crosslinked product having an average particle size of 400 μm, and 100 g of methanol was absorbed in 20 g of this to obtain a fuel composition (A1).

[Examples 1-3]
The methanol clathrate compound or fuel composition (A1) obtained in Production Examples 1 to 3 is filled in the fuel storage part 2 of the fuel cell fuel supply device 1 shown in FIG. In each case, an aqueous methanol solution was produced by pressing the sponge containing, and by injecting this aqueous methanol solution into the fuel cell test apparatus, the fuel cell could generate electricity.

  In addition, even when this fuel cell fuel supply device was dropped from a height of 1 m, no water leakage occurred, and the fuel cell could be similarly generated even when left at room temperature for 48 hours.

1 is a perspective view schematically showing a fuel supply device for a fuel cell according to a first embodiment of the present invention. It is a longitudinal cross-sectional view of the fuel supply apparatus for fuel cells which concerns on the 1st Embodiment of this invention. It is a perspective view which shows roughly the fuel supply apparatus for fuel cells which concerns on the 2nd Embodiment of this invention. It is a longitudinal cross-sectional view of the fuel supply apparatus for fuel cells which concerns on the 2nd Embodiment of this invention. It is a perspective view which shows roughly the fuel supply apparatus for fuel cells which concerns on the 3rd Embodiment of this invention. It is a longitudinal cross-sectional view of the fuel supply apparatus for fuel cells which concerns on the 3rd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,11,12 Fuel supply device for fuel cells 2,12,22 Fuel storage part 3 Flow means 5,27 Methanol clathrate compound (fuel composition, immobilized fuel)
6 Sponge (flowing means)
7, 13, 23 Push button (flowing means)
16 Fuel capsule (fixed fuel)

Claims (6)

A fuel storage unit in which a liquid fuel component is fixed;
Fluid means for fluidizing the fuel in the fuel storage section,
A fuel supply device for a fuel cell, wherein the liquid fuel component is made to flow by the flow means so that the liquid fuel component can be supplied to the fuel cell. The fuel storage portion stores a fuel composition for a fuel cell that is released from fuel by contact with water,
The flow means is a moisture supply device;
2. An aqueous solution of the fuel for the fuel cell is created by supplying water from the moisture supply device to the fuel storage unit, and the aqueous fuel can be supplied to the fuel cell. Fuel cell fuel supply device. The fuel storage part can be increased or decreased in volume, and the fuel storage part is filled with a microcapsule containing fuel for a fuel cell,
The flow means is a pressing body that changes the volume of the fuel storage portion,
2. The fuel cell according to claim 1, wherein when the volume of the fuel storage portion is reduced by the pressing body, the microcapsule is broken and the fuel cell fuel is discharged so that the fuel cell fuel can be supplied to the fuel cell. Fuel supply device for fuel cell. The volume of the fuel storage section can be increased or decreased. A fuel composition for a fuel cell that releases fuel by contacting the fuel storage section with water, and a microcapsule that stores water. Filled,
The flow means is a pressing body that changes the volume of the fuel storage portion,
When the volume of the fuel storage portion is reduced by the pressing body, the microcapsule is broken and water leaks, an aqueous solution of the fuel cell fuel is created, and the aqueous fuel can be supplied to the fuel cell. The fuel supply device for a fuel cell according to claim 1.   The fuel supply device for a fuel cell according to any one of claims 1 to 4, wherein the fuel storage unit includes a liquid fuel absorber. 6. The fuel cell fuel according to claim 1, wherein the fuel cell fuel is one or more selected from the group consisting of alcohols, ethers, hydrocarbons, and acetals. Fuel cell fuel supply device.

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