WO2006114929A1 - Fuel supply device for fuel cell - Google Patents

Abstract

A fuel supply device for a fuel cell, enabling fuel for a fuel cell to be safely carried and capable of simply supplying the fuel to the fuel cell. The fuel supply device (1) for a fuel cell has a fuel reception section (2) and a flow means (3) provided connected to the fuel reception section (2). The upper and the lower face of the fuel reception section (2) are covered with liquid pervious sheets (4, 4A), and the inside of the fuel reception section (2) is filled with a methanol clathrate (5). The flow means (3) is constructed by providing a push button (7) on the upper part of a water containing sponge (6) such that the button (7) can press the sponge (6). When the push button (7) is pressed to shrink (volume reduction) the sponge (6), the water is supplied to the fuel reception section (2) through the liquid permeable sheet (4) to produce fuel water solution.

Description

 Specification

 Fuel supply device for fuel cell

 Technical field

 [0001] The present invention relates to an apparatus for supplying fuel to a fuel cell.

 Background art

 [0002] A solid polymer electrolyte fuel cell is formed by using 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 surfaces of the membrane, and hydrogen or It is a device that generates oxygen by electrochemical reaction by supplying oxygen to methanol and power sword. The electrochemical reaction that occurs at each electrode is as follows:

 CH OH + H 0 → 6H + + CO + 6e "'· · [1]

 3 2 2

 And in the power sword,

3/20 + 6H ⁺ + 6e "→ 3H O---[2]

 twenty two

 It is. In order to cause this reaction, both electrodes are composed of a mixture of fine carbon 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. Then, electrons and hydrogen ions are generated by the reaction of the above 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 force sword and electrons flowing from the external circuit, as shown in the above reaction formula [2]. Produces water. On the other hand, electrons released from methanol are led to the external circuit through the catalyst carrier in the anode, and flow into the force sword from the external circuit. As a result, in the external circuit, electrons flow from the anode to the force sword and power is extracted.

 [0004] In recent years, direct methanol fuel cells using methanol as a fuel are likely to be applicable as portable small fuel cells. In recent years, development is actively underway as next-generation secondary batteries for portable computers and mobile phones. It's becoming.

[0005] However, the fuel of the direct methanol fuel cell uses methanol as a liquid. As a result, there are many handling problems that are very dangerous. As a method for safely storing such a fuel, a method in which the fuel is a molecular compound (see Patent Document 1), a method in which the fuel is absorbed into a polymer (see Patent Document 2), a fatty acid ester of a polyhydric alcohol, A method of blending (see Patent Document 3) has been reported. In addition, as a method for releasing fuel cell fuel from those fuel cell fuels having stable compositions, it has been reported that water is passed through the fuel composition to release it.

 Patent Document 1: International Publication 2004Z000857 pamphlet

 Patent Document 2: JP 2004-127659 A

 Patent Document 3: Japanese Patent Application Laid-Open No. 8-231970

 Disclosure of the invention

 Problems to be solved by the invention

[0006] However, in the conventional fuel discharge device, the water passing through the container containing the fuel composition for the fuel cell exists as a liquid, and the water leaks. There is a risk of doing it.

 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.

 Means for solving the problem

 [0008] A fuel supply device for a fuel cell according to the present invention includes a fuel storage unit in which a liquid fuel component is fixed, and a flow unit for flowing the fuel in the fuel storage unit, and the liquid fuel component is flowed by the flow unit. Thus, the liquid fuel component can be supplied to the fuel cell (Invention 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 to supply the liquid fuel component to the fuel cell. it can.

[0009] The fuel storage section stores a fuel cell fuel composition that is released from the fuel cell fuel by contact with water, the flow means is a water supply device, and the water supply device By supplying water to the fuel storage section, an aqueous solution of the fuel cell fuel can be prepared, and the aqueous fuel can be supplied to the fuel cell!ヽ (Departure [0010] Further, the volume of the fuel storage section can be increased or decreased, and the fuel storage section is filled with microcapsules that store fuel for fuel cells, and the flow means has a capacity 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. ! ヽ (Invention 3).

[0011] Further, the volume of the fuel storage section can be increased or decreased. The fuel storage section stores water and the fuel composition for the fuel cell that is released from the fuel cell fuel by contacting the fuel storage section with 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 micro force process is damaged. Water leaks and an aqueous solution of fuel for the fuel cell is created.

It is also possible to supply pressure to the fuel cell in the aqueous fuel (Invention 4).

[0012] In such a fuel cell fuel supply device (Inventions 1 to 4), the fuel storage section may include a liquid fuel absorber (Invention 5).

[0013] Further, in such a fuel cell fuel supply device (Inventions 1 to 5), the fuel for the fuel cell is selected from a group power consisting of alcohols, ethers, hydrocarbons, and acetals. 1 type or 2 types or more can be used (Invention 6).

 The invention's effect

 In the fuel supply device for a fuel cell according to 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. The liquid does not leak from the fuel storage part. By absorbing water into the fuel storage section, the fuel for the fuel cell can be easily released from the fuel composition containing the fuel for the fuel cell without requiring a heating device or heating energy.

 [0015] For this reason, the fuel for the fuel cell, which is difficult to handle, is stored safely and stably as a fuel composition containing the fuel for the fuel cell, and then the fuel for the fuel cell is easily and inexpensively taken out from the fuel composition. be able to.

[0016] Of the fuel for fuel cells, the methanol stock solution corresponds to a deleterious substance under the Poisonous and Deleterious Substances Control Law, and corresponds to a dangerous substance class 4 and must be handled with great care. Because methanol has problems such as corrosion in high concentration methanol, methanol is used as a fuel. In general, it is used as an aqueous solution of about 10 to 30% by mass. Therefore, it has been proposed to carry a cartridge of methanol aqueous solution as a general method, but preventing leakage of the aqueous solution has been a major problem. In the present invention, when the fuel composition is used, the fuel can be supplied to the fuel cell as an aqueous solution having an appropriate concentration by contacting the water with water and releasing the fuel in the fuel composition into the water. It is.

 Brief Description of Drawings

 FIG. 1 is a perspective view schematically showing a fuel cell fuel supply device according to a first embodiment of the present invention.

 FIG. 2 is a longitudinal sectional view of the fuel supply device for a fuel cell according to the first embodiment of the present invention.

 FIG. 3 is a perspective view schematically showing a fuel cell fuel supply device according to a second embodiment of the present invention.

 FIG. 4 is a longitudinal sectional view of a fuel supply device for a fuel cell according to a second embodiment of the present invention.

 FIG. 5 is a perspective view schematically showing a fuel cell fuel supply device according to a third embodiment of the present invention.

 FIG. 6 is a longitudinal sectional view of a fuel cell fuel supply device according to a third embodiment of the present invention.

 Explanation of symbols

[0018] 1, 11, 12... Fuel supply device for fuel cell

 2. 12, 22 ... Fuel storage

 3 ... Flowing means

 5, 27 ··· Methanol inclusion compound (fuel composition, immobilized fuel)

 6 ··· Sponge (fluid means)

 7. 13, 23… Push button (fluid means)

 16 ·· 'Fuel capsule (fixed fuel)

 BEST MODE FOR CARRYING OUT THE INVENTION

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

In FIG. 1 and FIG. 2, the fuel cell fuel supply device 1 includes a fuel storage portion 2 and a flow means 3 provided in connection with the storage portion 2. The upper and lower surfaces of the fuel storage unit 2 are covered with the liquid permeable sheets 4 and 4A, and the methanol inclusion compound 5 is filled inside. As described above, in this embodiment, methanol, which is a liquid fuel component, is used as an inclusion compound so that it can be fixed and can be safely carried. Further, the flow means 3 is configured by attaching a push button 7 to an upper part of a sponge 6 containing water and the sponge 6 so that it can be pressed and deformed. The fuel container 2 communicates with the fuel electrode (not shown) of the direct methanol fuel cell via a liquid-permeable sheet 4A covering the lower side.

 In such a fuel cell fuel supply device 1 of the present embodiment, when the push button 7 is pressed to reduce (decrease) the sponge 6, water passes through the liquid permeable sheet 4. Supplied to the fuel storage part 2. When this water comes into contact with the methanol clathrate compound 5, fuel for the 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 from the lower liquid-permeable sheet 4A by 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 based on FIG. 3 and FIG.

 3 and 4, the fuel supply device 11 for the fuel cell includes a fuel storage portion 12 and a push button 13 as the flow means 3 provided to be connected to 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. A fuel capsule 16 in which an aqueous methanol solution, which is a liquid fuel component, is enclosed. Filled. 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 container 12 communicates with a fuel electrode (not shown) of a direct methanol fuel cell via a liquid-permeable sheet 15 covering the lower side! /

In such a fuel cell fuel supply device 11 of this embodiment, when the push button 13 is pressed, the flexible sheet 14 is held without breaking, and the push button 13 is brought into the fuel storage portion 12. Push As a result, the volume of the fuel container 12 is reduced, the fuel capsule 16 is pressure damaged, and the methanol aqueous solution leaks, and the methanol aqueous solution, which is the fuel solution for the fuel cell, is reduced by the pressure due to the penetration of the push button 13. Out of the liquid-permeable sheet 15 on the side and supplied to the fuel electrode of the fuel cell.

 Furthermore, a third embodiment of the present invention will be described based on FIG. 5 and FIG.

 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 in connection with 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 containing water inside and a methanol inclusion compound 27 And are filled. As described above, according to the present embodiment, methanol, which is a liquid fuel component, is used as an inclusion compound, and water is sealed in the capsule to fix the liquid fuel component. It has become portable. The fuel container 22 communicates with a fuel electrode (not shown) of a direct methanol fuel cell through 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 crushed without breaking, and the push button 23 is moved to the fuel accommodating portion 22. When pushed in, the volume of the fuel container 22 is reduced, the water capsule 26 is pressure-dissipated and water leaks, and comes into contact with the hydraulic power tank inclusion compound 27 to form a methanol aqueous solution. A fuel solution for the fuel cell is produced. The aqueous methanol solution which is the fuel solution for the fuel cell flows out from the lower liquid-permeable sheet 25 due to the pressure due to the penetration of the push button 23 and is supplied to the fuel electrode of the fuel cell.

[0026] In the second and third embodiments described above, a liquid fuel absorber such as a sponge lump is mixed in the fuel storage portions 12 and 22 so as to be pushed when the power supply by the fuel cell is stopped. When the pressing by the buttons 13 and 23 is released, the liquid fuel absorber such as a sponge lump expands, and the excess liquid in the fuel storage portions 12 and 22 can be absorbed. Note that the liquid fuel absorber does not absorb the liquid when pressed, but it is preferable to reduce the pressure so that the liquid can be absorbed.For example, the liquid can be absorbed by controlling the pressure. Responding to pressure using a changing polymer absorber or using a thermosensitive gel You can control the temperature.

 [0027] In the first to third embodiments as described above, the fuel for fuel cell (or liquid fuel component) is a force that can include alcohols, ethers, hydrocarbons, or acetals. It is not limited to these as long as it can be used as a fuel for a polymer electrolyte fuel cell. Specifically, alcohols such as hydrogen, methanol, ethanol, n-propanol, isopropanol, and ethylene glycol; ethers such as dimethyl ether, methyl ether, and jetyl ether; hydrocarbons such as propane and butane; dimethoxymethane, trime Forces including acetals such as toshikimethane are not limited to these, and these may be used alone or in combination of two or more.

 [0028] The fuel cell is preferably a solid polymer fuel cell. Among them, a direct methanol fuel cell is suitable, but is not limited thereto.

 [0029] The fuel cell fuel may be a fuel cell fuel composition that is solid or gelled as a molecular compound or polymer of the fuel cell fuel.

 [0030] The molecular compound means that two or more kinds of compounds that can exist stably alone are relatively weak interactions other than covalent bonds, such as hydrogen bonds and van der Waals forces. These are bonded compounds, and include hydrates, solvates, addition compounds, and inclusion compounds. Such molecular compounds can be formed by the 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. Fuel cell fuel can be stored in

 [0031] Examples of the molecular compound include clathrate compounds in which the fuel for the fuel cell is clathrated by the contact reaction between the host compound and the fuel for the fuel cell.

[0032] Among the molecular compounds, as the host compound that forms the clathrate compound that clathrates the fuel for the fuel cell, a compound composed of an organic compound, an inorganic compound, and an organic / inorganic composite compound is known. In addition, as organic compounds, monomolecular, polymolecular, and polymeric hosts are known.

[0033] Monomolecular hosts include cyclodextrins, crown ethers, cryptands, Examples include cyclophanes, azacyclophanes, calixarenes, cyclotriveratrylenes, spherands, and cyclic oligopeptides. Multimolecular hosts include urines, thioureas, deoxycholic acids, cholic acids, perhydrotriphenylenes, trio-thymotides, bianthryls, spirobifluorenes, and cyclophosphazenes. Monoalcohols, diols, hydroxybenzophenones, acetylene alcohols, phenols, bisphenols, trisphenols, tetrakisphenols, polyphenols, naphthols, bisnaphthols, diphenol methanol, Examples thereof include carboxylic acid amides, thioamides, bixanthenes, carboxylic acids, imidazoles, and hydroquinones. Polymeric hosts include celluloses, starches, chitins, chitosans, polybutyl alcohols, polyethylene glycol arm polymers with 1, 1, 2, 2, —tetrakis-pheulethane as the core. , _Α , α, α ′, α, polyethylene glycol arm type polymers having tetra-tetraxylene xylene as a core. In addition, organic phosphorus compounds, organic silicon compounds, and the like are also included.

 [0034] 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 And porous glass.

 [0035] Furthermore, some organometallic compounds exhibit properties as host compounds, such as organoaluminum compounds, organotitanium compounds, organoboron compounds, organozinc compounds, organoindium compounds, organogallium compounds, organic Examples include tellurium compounds, organotin compounds, organozirconium compounds, and organomagnesium compounds. Moreover, it is possible to use a metal salt of an organic carboxylic acid, an organometallic complex, or the like, but it is not particularly limited as long as it is an organometallic compound.

 [0036] Among these host compounds, a multimolecular host whose inclusion ability is not easily influenced by the size of the guest compound molecule is more effective.

[0037] 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-Dimethylphenol) — 2 —Propin 1 1-Honole, 1, 1, 4, 4, —Tetraphenol 2 1—Butyne 1,4-Diol 1, 1, 6, 6, —Tetrakis (2, 4, —Dimethylphenol) 1, 2, 4—Hexadiyne 1, 6 Diol, 9, 10 Diphenol 9,10 Dihydroanthracene 9,10 Diol, 9, 10 Bis (4-methylphenol) 9,10 Dihydroanthracene 9,10 Diol 1, 1, 2, 2 —Tetraphenol-lethane 1,2 diol, 4-methoxyphenol, 2,4-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 1, 1-bis (4 hydroxyphenyl) cyclohexane, 4, 4'-sulfol bisphenol, 2, 2, 1-methylene bis (4-methyl 6-tert-butyl phenol), 4, 4, Denbisphenol, 4, 4, -thiobis (3-methyl-6-t-butylphenol), 1, 1, 3 Tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane, 1, 1, 2, 2-tetrakis (4 hydroxyphenol) ethane, 1, 1, 2, 2 Te tetrakis (4-hydroxy Hue - Le) ethylene, 1, 1, 2, 2- tetrakis (3-methyl-4 human Dorokishifueniru) Etan, 1, 1, 2, 2-tetrakis (3 Furuoro 4-hydroxy-phenylene Le) Etan, _a , a, α ', α, one tetrakis (4-hydroxyphenol) one ρ xylene, 3, 6, 3', 6 '-tetramethoxy 9, 9' be 9Η-xanthene, 3, 6, 3 '6'—Totracetoxy-9,9, 1B 9Η-Xanthene, gallic acid, methyl gallate, catechin, bis j8-naphthol, a, a, α', α, 1 tetraphenyl 1, 1, 1 biphenol -1, 2, 2, 1-dimethanol, diphenic acid bis (dicyclohexylamide), fumaric acid bis (dicyclohexylamide), cholic acid, deoxycholic acid, 1, 1, 2, 2-tetrakis (4 carboxyphenol- Le) ethane, 1, 1, 2, 2-tetrakis (3-carboxyph -Ru) ethane, acetylenedicarboxylic acid, 2, 4, 5 triphenylimidazole, 1, 2, 4, 5—tetraphenyl imidazole, 2 phenol phenant mouth [9, 10—d] imidazole, 2— (o cyanophane) phenant mouth [9, 10—d] imidazole, 2-— (m-sianophenol) phenant mouth [9, 10— d] imidazole, 2-— (p cyanophenol) phenant mouth [9 , 10 d] imidazole, hydroquinone, 2-t-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5 bis (2,4-dimethylphenol) hydroquinone, etc. 1, 1— A phenolic host compound such as bis (4-hydroxyphenol) cyclohexane is advantageous in terms of easy industrial use.

These host compounds may be used alone or in combination of two or more. These host compounds form solid inclusion compounds with fuels for fuel cells. As long as the compound has any shape,

 [0039] The above-mentioned organic host compound 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 intercalation compounds such as clay minerals and montmorillonites in addition to silicas, zeolites and activated carbons, but are not limited thereto. Absent.

 [0040] Such an organic / inorganic composite material is, for example, dissolved in a solvent capable of dissolving the above-mentioned organic host compound, impregnated with the solution in an inorganic porous material, dried and dried under reduced pressure. It can be manufactured from Tsujiko. The amount of the organic host compound supported on the inorganic porous material is not particularly limited, but is usually about 10 to 80% by mass with respect to the inorganic porous material.

 [0041] Examples of a method for synthesizing a fuel cell fuel inclusion compound using a host compound such as 1,1 bis (4-hydroxyphenol) cyclohexane described above include a fuel cell fuel and a host compound. For example, a method in which the host compound is directly contacted and mixed, and a method in which the host compound is dissolved and recrystallized by heating the fuel for the fuel cell. In addition, when the fuel for the fuel cell is a gas or a liquid, the inclusion compound of the fuel for the fuel cell can be obtained by contacting the fuel with the host compound in a pressurized state.

 [0042] The temperature at which the fuel for the fuel cell and the host compound are brought into contact with each other is not particularly limited, but is preferably from room temperature to about 100 ° C. Further, the time for contacting the fuel for the fuel cell and the host compound is not particularly limited, but is preferably about 0.01 to 24 hours from the viewpoint of work efficiency.

 [0043] 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 cell fuel is used, A liquid mixture of fuel for fuel cells and other components may be used.

[0044] 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., but usually one mole of the host compound is used. On the other hand, it is an inclusion complex containing 0.1 to 10 mol of fuel molecules for fuel cells.

[0045] The clathrate compound thus obtained can stably store fuel for fuel cells for a long period of time in a normal temperature / normal pressure environment. However, this inclusion is lightweight and handled. Since it has excellent properties and strength, it can be easily stored in a glass, metal, plastic, or other container, eliminating the problem of liquid leakage. In addition, the liquid fuel usually becomes solid due to the inclusion, so that the property as a deleterious substance or dangerous substance can be avoided. Furthermore, the chemical reactivity of fuel for fuel cells can be reduced, and for example, the corrosiveness to metals can be alleviated.

 [0046] The fuel composition contains 20 to LOO% by mass of a structural unit having a carboxyl group and Z or sulfonic acid group in the molecule based on the polymer (1), and the carboxyl group and / or the 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 of a sulfonic acid group 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 Z or sulfonic acid group in the molecule, and the carboxyl group and Z or sulfonic acid Proton power of group A cross-linked product (A) of the polymer (1) substituted with a predetermined amount of cation is used.

 [0047] Structural unit having carboxyl group and Z or sulfonic acid group constituting crosslinked body (A)

 As (a), a monomer having a carboxyl group [for example, (meth) acrylic acid, etaatalic acid, crotonic acid, sorbic acid, maleic acid, itaconic acid, fumaric acid, cinnamic acid, and anhydrides thereof Etc.]; Monomers having a sulfonic acid group [for example, aliphatic vinyl sulfonic acids [Bulsulfonic acid, allylic sulfonic acid, butyltoluenesulfonic acid, styrenesulfonic acid, etc.], (meth) acrylate sulfonic acid [sulfoethyl (meth) attaly Rate, sulfopropyl (meth) acrylate, etc.) and (meth) acrylamide type sulfonic acids [for example, acrylamide 2-methylpropane sulfonic acid, etc.], etc., and one or more of these are polymerized (1 ). A structural unit having a carboxyl group having 3 to 30 carbon atoms and Z or a sulfonic acid group is preferred.

[0048] As a method of obtaining a polymer (1) containing a predetermined amount of a structural unit having a carboxyl group and Z or a sulfonic acid group in the molecule, in addition to a method of polymerizing the monomer (a) in a predetermined amount. For example, a monomer that can be easily changed to a carboxyl group or a sulfonic group, such as an esterified product or an amidated product of the carboxyl group or sulfonic acid group-containing monomer, is polymerized, and a method such as hydrolysis is used. Quantitative carboxyl group sulfonate group In addition, the polymer (1) includes a high molecular weight carboxyl group represented by carboxymethyl cellulose, a high molecular weight polysaccharide-containing polysaccharide, and the high molecular weight of the polysaccharide. A force that can exemplify a graft copolymer of a molecule and another monomer, etc. There is no particular limitation as long as a polymer containing a predetermined amount of structural units of carboxyl group and Z or sulfonic acid group is finally obtained. .

[0049] The content of the polymer (1) of the constituent unit having a carboxyl group and Z or sulfonic acid group, usually. 20 to: LOO mass _^0/0, preferably 40 to: LOO mass _^0/0, more preferably Is 60: LO 0% by mass. If the content is less than 20%, even if the proton of the carboxyl group or sulfonic acid group is replaced with a cation cation described later, the absorption amount to the target liquid fuel decreases, or if the amount is small, the liquid fuel is gelled. There are cases where it is not possible.

[0050] Examples of the copolymerizable monomer (b) that forms a structural unit other than the structural unit having a carboxyl group and Z or a sulfonic acid group include, for example, an alkyl (meth) acrylate (having 1 to 30 carbon atoms) ester. [Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethyl hexyl (meth) acrylate, octyl (meth) acrylate, ( (Meth) acrylic acid dodecyl, (meth) acrylic acid stearyl, (meth) acrylic acid file, (meth) acrylic acid octyl file, (meth) acrylic acid cyclohexyl, etc.]; (meth) acrylic acid oxyalkyl ( Carbon number 1-4) [(Meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl, (meth) acrylic acid mono (polyethylene glycol) ester ( PEG number average molecular weight: 100-4000), (meth) acrylic acid mono (polypropylene glycol) ester (PPG number average molecular weight: 100-4000), (meth) acrylic acid monomethoxypolyethylene glycol (PEG number average molecular weight: 100-4000) ), (Meth) acrylic acid monomethoxypropylene glycol (PPG number average molecular weight: 100 to 4000), etc.]; (meth) acryl amides [(meth) acrylamide, (di) methyl (meth) acrylamide, (di) ethyl ( (Meth) Atarylamide, (di) propyl (meth) acrylamide, etc.]; allylic ethers [methylaryl etherate, ethenorea linoleatenore, propinoare linoleatenore, glycerono monomono enoleate, trimethylol Propane triallyl ether, pentaerythritol monoallyl ether, etc.]; α-o having 4 to 20 carbon atoms Refines [isobutylene, 1-hexene, 1-otaten, isootaten, 1-nonene, 1-decene, 1-dodecene, etc.]; aromatic bi-carbons with 8 to 20 carbon atoms [Styrene, t-butyl styrene, octyl styrene, etc.]; Other vinyl compounds [N-Bulucacetamide, caproic acid butyl, lauric acid butyl, stearic acid vinyl, etc.]; Amino group-containing monomers [ Dialkyl (carbon number of alkyl: 1 to 5) aminoethyl (meth) atalylate, meta (attalyloyl) oxytyltrialkyl (alkyl number of carbon: 1 to 5) ammonium chloride, bromide or sulfate]; Examples thereof include alkali metal salts of monomers having a carboxyl group and a sulfonic acid group; primary to tertiary amine amines; One or more of these monomers (b) may be copolymerized with the above-mentioned (a) within a predetermined range (less than 80% of the polymer structural units) if necessary!

[0051] Among the monomers (b), from the viewpoint of the polymerizability of the monomers and the stability of the produced polymer, (meth) acrylic acid alkyl esters, oxyalkyl (meth) acrylates, aryl ethers, _A- olefins and aromatic vinyl compounds are preferred.

 [0052] Monomer (b) whose difference between SP value of solvent and monomer (b) is 5 or less is selected according to the SP value (solubility parameter) of the solvent to be absorbed or gelled of liquid fuel It is more preferable to select a solvent having an SP value of 3 or less as the SP value of the target solvent and the SP value of the monomer (b) because the absorbed amount tends to increase the gel repulsion.

[0053] The proton of the carboxyl group and Z or sulfonic acid group O - it is desirable to 30-100 mole _^0/0 substituted with Umukachion. As the cation cation, the quaternary ammonium cation (1), the tertiary sulfo cation (11), the quaternary phospho cation (111), and the tertiary oxo cation (IV) group of cations One or more selected from

[0054] Examples of the quaternary ammonia cation (I) include the following (1-1) to (1-11).

 (1-1) Aliphatic quaternary ammonium having 4 to 30 or more carbon atoms having an alkyl and Z or alkenyl group; tetramethyl ammonium, ethyl trimethyl ammonium, Jetyldimethyl ammonium, triethyl methyl ammonium, tetraethyl ammonium, trimethylpropyl ammonium, tetrapropyl ammonium, butyl trimethyl ammonium, tetraptyl ammonium, etc. .

[0055] (1-2) Aromatic quaternary ammonia having 6 to 30 or more carbon atoms; trimethylphenol, dimethylethylamine, dimethylethylamine, triethylylamine Mu etc.

 [0056] (I-3) Cycloaliphatic quaternary ammonium having 3 to 30 or more carbon atoms; N, N-dimethylpyrrolidinium, N ethyl N-methylpyrrolidinium, N, N Dimethyl morpholine, N, N Jetyl morpholium, N, N dimethyl piperidium, N, N dimethyl biverium, etc.

 [0057] (1-4) imidazolium having 3 to 30 or more carbon atoms; 1, 2, 3 trimethylimidazolium, 1, 2, 3, 4-tetramethylimidazolium, 1, 3, 4 Trimethyl-2 ethylimidazolium, 1,2 dimethyl-3, 4 Jetylimidazolium, 1,2 dimethyl-3 ethylimidazolium, 1-ethyl-3-methylimidazolium, 1, 2, 3, 4—Tetratilimidazolium, 1, 2, 3 Triethylimidazolium, 4 Cyan—1, 2, 3 —Trimethylimidazolium, 2 Cyanmethyl 1, 3 Dimethylimidazole, 4--Acetyl-1, 2, 3 Trimethylimidazole, 4-Methylcarboxymethyl-1, 2, 3 Trimethylimidazole, 4 Formyl-1, 2, 3 Trimethylimidazole, 3-hydroxyethyl 1, 2, 3 Trimethylimidazole, 3-hydroxyethyl 1, 2, dimethyl imidazolium, etc.

 [0058] (1-5) Imidazolium having 3 to 30 or more carbon atoms; 1, 3 Dimethylimidazolium, 1-Ethinole 1-Metinorei Midorium, 1-Metinore 1 3-Ethinorei Midazolium 1,2,3,4-tetramethylimidazolium, 1,2 dimethyl-3-ethylimidazolium, 1-echi nore 1-methinoreido imidazolium, 1-methinorei 1-ethinorei imidazolium, 1, 2, 3 Trie til imidazolium, 1, 2, 3, 4—tetraethyl imidazolium, 1, 3 dimethyl—2 ferro-imidazolium, 1, 3 dimethyl 1-2 benzyl imidazolium, 4 siano 1, 2,3 Trimethylimidazole, 3 Cyanmethyl 1,2 Dimethylimidazole, 4 Cetinore 1,2,3 Trimethylimidazole, 4-Methoxy-1,2,3 Trimethylimidazolium, 3 Formylmethyl-1 , 2 Louis imidazolium, 2-hydroxyethyl 1,3—dimethylimidazolium, N, N, -dimethylbenzimidazolium, N, N, monoethylbenzimidazolium, N—methyl-N, 1 benzylbenzimidazolium etc.

[0059] (1-6) Tetrahydropyrimidinium having 4 to 30 or more carbon atoms; 1, 3 dimethyltetrahydropyrimidinium, 1, 2, 3 trimethinoletetrahydropyrimidinium, 1 , 2, 3, 4-tet Lamethyltetrahydropyrimidium, 8—methyl 1,8 diazabicyclo [5, 4, 0]-7 —Undesseum, 5-methyl-1,5 diazabicyclo [4, 3, 0] — 5 None , 3-cyanomethyl-1,2 dimethyltetrahydropyrimidime, 3 acetylmethyl-1,2 dimethyltetrahydropyrimidime, 4 methylcarboxymethyl-1,2,3 trimethyltetrahydropyrimidime, 3-methoxy Methyl-1,2 dimethyltetrahydropyrimidinium, 4-hydroxymethyl-1,3 dimethyltetrahydropyrimidinium, etc.

[0060] (1-7) Dihydropyrimidium having 4 to 30 or more carbon atoms; 1,3 dimethyl-2,4 or 2,6 dihydropyrimidium [these are 1,3 dimethyl-2,4 (6) Denoted as “jihido pyrimidum”, the same expression is used hereinafter. ], 1, 2, 3 Trimethyl-2,4 (6) -dihydropyrimidium, 1,2,3,4-tetramethyl-2,4 (6) -dihydropyrimididium, 1, 2, 3, 5—Tetramethinole 2, 4 (6) —Dihydropymidyureum, 8—Methinore 1,8—Diazacyclo [5, 4, 0] — 7, 9 (10) —Undecangeum, 2 Cyanmethyl-1,3 Dimethyl 2, 4 (6) —Dihydropyrimidium, 3 acetylmethyl-1, 2 dimethyl —2, 4 (6) —Dihydropyrimidium, 4-methylcarboxymethyl 1, 2, 3 Trimethylol 2, 4 (6 ) —Dihydropyrimidinium, 4 Honoremino 1, 2, 3 Trimethinole 2, 4 (6) —Dihydropyrimidium, 3 Hydroxyethyl 1, 2 Dimethyl 2, 4 (6) —Dihydropyrimidin Mu etc.

[0061] (I 8) Guanidium having an imidazolinium skeleton having 3 to 30 or more carbon atoms; 2 —dimethylamino-1, 3, 4 trimethylimidazole, 2 jetylamino-1, 3, 4 —trimethylimidazoli 1-methyl 3,4 dimethyl imidazole, 2 dimethylamino 1,3 dimethyl imidazole, 2 dimethylamino 1,3 dimethyl imidazolium, 2 jetinoreamino 1,3 Tyrimidazolium, 1, 5, 6, 7-tetrahydro 1,2 dimethyl-2H-pyrimido [1, 2a] imidazole, 1,5 dihydro-1,2 dimethyl-2H-pyrimido [1, 2a] Imidazole, 2 Dimethylamino 3 Methylcarboxymethyl 1-Methyl imidazolium, 2 Dimethylamino 3-Methoxymethyl-1-methyl imidazolium, 2-Dimethylamino 3 Hydro Shechiru 1-methyl imidazolium - © beam, 2 Jimechiruamino one 4-hydroxymethyl-one 1, 3-dimethyl imidazolinium - © beam or the like. [0062] (I 9) Guanidium having an imidazolium skeleton having 3 to 30 or more carbon atoms; 2-dimethylamino-1, 3, 3, 4 trimethylimidazolium, 2 jettilamino-1, 3, 4 trimethylimidazolium, 2 Jetylamino-1, 3 Dimethyl-4-ethylimidazolium, 2 Jetylamino-1, 3, 4 Triethylimidazole, 2 Dimethylamino-1, 3, 3-Dimethinoleyimidazolium, 1, 5, 6, 7-Tetrahydro 1,2 Dimethylolone 2H—imide [1, 2 a] imidazole, 1,5 dihydro-1,2 dimethyl-2H—pyrimido [1, 2a] imidazole, 2 dimethylamino-3 cyanomethyl-1-methyl imidazolium, 2 Dimethylamino 4 Methylcarboxymethyl-1,3 Dimethylimidazole, 2 Dimethylamino-3 Methoxymethyl-1-Methylimidazolium, 2-Dimethyl Ruamino 3 Horumirumechi Lou 1-methyl imidazo Riu arm, 2 Jimechiruamino one 4-hydroxymethyl-one 1, 3 dimethyl chill imidazolium like.

 [0063] (I-10) Gua-dium having a tetrahydropyrimidi-um skeleton having 4 to 30 or more carbon atoms; 2 Dimethylamino-1, 3, 4 Trimethyltetrahydropyrimidium, 2 Jettyamino 1 , 3, 4 Trimethyltetrahydropyrimidium, 2 Dimethylamino-1,3-dimethyltetrahydropyrimidium, 2 Jetylamino-1,3 Dimethyltetrahydropyrimidium, 1, 3, 4, 6, 7, 8 Hexahydro 1,2 dimethyl— 2H—imide [1, 2 a] pyrimidium, 1, 3, 4, 6, 7, 8 Hexahydro 1,2 dimethyl 1 2H pyrimido [1,2a] pyrimidium 2 dimethylamino 1-cyanomethyl 1-methyltetrahydropyrimidium, 2 dimethylamino-4 acetyl-1,3 dimethyltetrahydropyrimidium 2 dimethylamino-4 methylcarboxymethyl-1,3 dimethyltetrahydride Ropyrimidium, 2 Dimethylamino-1-3-Methylmethyl-1-methyltetrahydropyrimidium, 2 Dimethylamino-1-hydroxyethyl 1-methyltetrahydropyrimidinium, 2-Dimethylamino-4-hydroxymethyl-1- 1 , 3 Dimethyltetrahydropyrimidinium, etc.

[0064] (I11) Guadium having a dihydropyrimidi-um skeleton having 4 to 30 or more carbon atoms; 2 Dimethinoreamino-1, 3, 4-trimethinole 2, 4 (6) -Dihydropyrimige 1-, 3- and 4- (3) trimethyl 2,4 (6) —dihydropyrimidium, 2,3,4-triethylinole 2,4 (6) —dihydropyrimidium, 2 jetinoreamino-1 , 3 Dimethyl 2, 4 (6) —Dihydropyrimidium, 2 Dimethylamino 1— 1-methylol 2,4 (6) -dihydropyrimidinium 1, 6, 7, 8-tetrahydro 1,2-dimethyl 1H-imide [1, 2a] pyrimidium 1, 6 Dihydro-1,2, dimethyl-1,2H —pyrimido [1, 2a] pyrimidium, 2 dimethylamino-1,4 cyano-1,3 dimethyl-1,2,4 (6) —Dihydropyrimidium, 2 dimethylamino3 acetylmethyl-1—methyl- 2, 4 (6) —Dihydropyrimidium, 2 dimethylamino 1-methylcarboxymethyl — 1-methyl 2, 4 (6) —Dihydropyrimidium, 2 dimethylamino 1 4 Formyl 1, 3 Dimethinole 1, 2 (6) —Dihydropyrimidium, 2 Dimethinoreamino-1, 3 Honoleminoremethyl 1-Methyl 2, 4 (6) —Dihydropyrimidi-um, etc.

 [0065] Examples of the tertiary sulfoyuium cation (II) include the following (II 1) to (II 3).

 (II-1) Aliphatic tertiary sulfonium having an alkyl having 1 to 30 or more carbon atoms and a Z or alkenyl group; trimethylsulfum, triethylsulfum, ethyldimethylsulfum, jetyl Methyl sulfo-um and the like.

 [0066] (II 2) Aromatic tertiary sulfone having 6 to 30 or more carbon atoms; Fehr-dimethi nolesnorehonum, Hue-norechinoremethinoresnorehonium, Hue -Noremetino Lebenzinoles Norejo

-Um etc.

 [0067] (II 3) Alicyclic tert-sulfoium having 3 to 30 or more carbon atoms; methylthiolaum

, Felt thiolum, methyl thiarum, etc.

[0068] Examples of the quaternary phosphonium cation (III) include the following (III 1) to (III 3).

 (III 1) Aliphatic quaternary phosphonium having 1 to 30 or more carbon atoms and Z or alkenyl groups; tetramethylphosphonium, tetraethylphosphonium, tetrapropy Norrephosphonium, Tetrabutinorephosphonium, Methyltritinorephosphonium, Methyltripropylphosphonium, Methyltributylphosphonium, Dimethyljetylphosphonium, Dimethyldibutylphosphonium, Trimethyl Ethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, etc.

[0069] (III 2) Aromatic quaternary phosphonium having 6 to 30 or more carbon atoms; triphenyl methole norephospho um, diphenol noresi methino rephospho um, triphenol nore veneno lesphospho -Um etc.

[0070] (III 3) An alicyclic quaternary phosphonium having 3 to 30 or more carbon atoms; 1,1-dimethylphosphine Suhoranimu, 1-Mechinore 1-etinorephosphoranium, 1, 1 Getinorephosphoranium

1, 1-jetyl phosphorinum, 1,1-pentaethylene phosphorinum, etc.

[0071] Examples of the tertiary oxoyuium cation (IV) include the following (IV-1) to (IV-3).

 (IV 1) Aliphatic tertiary oxoum having an alkyl having 1 to 30 or more carbon atoms and a Z or alkenyl group; trimethyloxoum, triethyloxoyuum, ethyldimethyloxo-sodium, jetylmethyloxo -Um etc.

[IV-2] Aromatic tertiary oxoyuum having 6 to 30 or more carbon atoms; ferrodimethyl oxomethyl, ferroethylmethyl oxodium, ferromethylbenzyloxo

-Um etc.

 [IV-3] Cycloaliphatic tertiary oxoyuum having 3 to 30 or more carbon atoms; methyl oxouranium, ferrosolum, methyloxa-um, etc.

 [0074] Among these, a preferred form cation is (I), and more preferred is (1-1),

 (1-4) and (1-5), and (1-4) and (1-5) are particularly preferred. These onion cations may be used alone or in combination of two or more.

 [0075] Examples of the method for introducing the form cation into the polymer include a method in which protons of the carboxyl group and Z or sulfonic acid group of the polymer are substituted with the form cation. Any method can be used to replace protons with the above-mentioned cation, as long as it is a method that can replace the cation with a predetermined amount. For example, a hydroxide salt of the above-mentioned cation (for example, tetraethyl cation). Ammonium hydroxide, etc.) monomethyl carbonate salts (eg 1, 2, 3, 4 trimethylimidazolium monomethyl carbonate, etc.) with high carboxyl group and Z or sulfonic acid group content. It can be easily replaced by adding it to the molecule and performing dehydration, decarboxylation, demethanol, etc. if necessary. Moreover, you may substitute similarly in the stage of a monomer.

[0076] With respect to the stage of substitution with the form cation, for example, a method in which the monomer containing the carboxyl group and Z or sulfonic acid group is substituted with the form cation and then polymerized, or the carboxyl group and Z or sulfonic group For example, there is a method of substituting the proton of the acid with an onion cation after the preparation of the polymer having the above, but if the final proton of the carboxyl group and the Z or sulfonic acid group is substituted, Z This may be done at this stage.

[0077] The proton of the carboxyl group and Z or sulfonic acid group O - degree of substitution by Umukachion (degree of substitution) is,. 30 to: LOO mol _^0/0, preferably 50 to: LOO mol _^0/0, more preferably the 70~: L00 is the mole _^0/0. O - With the degree of substitution Umukachion is less than 30 mole _^0/0, the carboxyl group of the polymer (1), sulfonic Sanmoto及Bio - sometimes swelling mosquito dissociation Umukachion is too low Ya Gerui匕力low.

 [0078] In the present invention, the structural unit having a carboxyl group and Z or a sulfonic acid group is quantitatively contained, and the carboxyl group and Z or the sulfonic acid group are substituted with a predetermined amount of formcation. The polymer (1) is finally crosslinked at any stage to form a crosslinked product. As a method for crosslinking, for example, the following methods [1] to [5] can be given which are well known in the art.

 [0079] [1] Cross-linking with copolymerizable cross-linking agent

 Two or more double bonds can be copolymerized with the carboxyl group- and Z- or sulfonic acid group-containing monomer, an cation-substituted cation of the monomer, and, if necessary, another monomer (b) to be copolymerized. Copolymerizable cross-linking agent [for example, polyvalent bur type cross-linking agent such as dibulebenzene, (meth) acrylamide type cross-linking agent such as N, N, -methylenebisacrylamide, and polyvalent allyl ether type such as pentaerythritol triallyl ether A method of cross-linking by crosslinking a polyvalent (meth) acrylic acid ester type cross-linking agent such as a cross-linking agent or trimethylolpropane tritalylate].

 [0080] [2] Cross-linking with reactive cross-linking agent

 A reactive cross-linking agent having two or more functional groups in the molecule that can react with a carboxyl group and a Z or sulfonic acid group or an organic cation substitution product thereof, or a functional group of a monomer to be copolymerized if necessary [for example, 4 , 4'-dimethanemethane diisocyanate and other polyisocyanate type crosslinking agents, polyglycerol polyglycidyl ether and other polyvalent epoxy type crosslinking agents, glycerin and other polyhydric alcohol type crosslinking agents, hexamethylenetetramine Or a polyvalent amine such as polyethylene imine, an imine type crosslinking agent, a haloepoxy type crosslinking agent such as epichlorohydrin, a polyvalent metal salt type crosslinking agent such as aluminum sulfate, etc.].

[0081] [3] Crosslinking with polymerization reactive crosslinking agent The carboxyl group and z- or sulfonic acid group-containing monomer, an cation-substituted cation of the monomer, and, if necessary, copolymerizable with another monomer (b) or having a double bond in the molecule, And a polymerizable reactive crosslinking agent having a functional group capable of reacting with a functional group of a carboxyl group and Z or a sulfonic acid group or a cation cation substitution product thereof, and, if necessary, a monomer to be copolymerized, if necessary [for example, glycidyl metatalylate And the like using a glycidyl (meth) acrylate-type cross-linking agent such as allylic epoxy type cross-linking agents such as allyl glycidyl ether.

 [0082] [4] Cross-linking by irradiation

 The polymer (1) is irradiated with radiation such as ultraviolet rays, electron beams and γ rays to crosslink the polymer (1), and the monomer is irradiated with ultraviolet rays, electron beams and γ rays to simultaneously polymerize and crosslink. How to do it.

[0083] [5] Crosslinking by heating

 A method in which the polymer (1) is heated to 100 ° C. or more and thermally crosslinked between the molecules of the polymer (1) (for example, crosslinking between carbons due to generation of radicals by heating or crosslinking between functional groups). etc.

[0084] Among these cross-linking methods, the preferred one varies depending on the use and form of the final product, but when considered comprehensively, [1] cross-linking with a copolymerizable cross-linking agent, [2] cross-linking with a reactive cross-linking agent and [4] Cross-linking by irradiation.

[0085] Among the copolymerizable crosslinking agents, preferred are polyvalent (meth) acrylamide type crosslinking agents, aryl ether type crosslinking agents, and polyvalent (meth) acrylic acid ester type crosslinking agents, and more preferred. One is a aryl ether type cross-linking agent.

[0086] Among the reactive crosslinking agents, preferred are polyvalent isocyanate type crosslinking agents and polyvalent epoxy type crosslinking agents, and more preferred are polyvalent isocyanate types having three or more functional groups in the molecule. It is a crosslinking agent or a polyvalent epoxy type crosslinking agent.

[0087] The degree of crosslinking can be appropriately selected depending on the purpose of use, but when a copolymerizable crosslinking agent is used, 0.001 to 10% by mass is preferable with respect to the total monomer mass.

More preferred is ˜5% by mass.

[0088] The amount of addition in the case of using a reactive crosslinking agent is such that the preferred amount of addition varies depending on the shape of the crosslinked body (A). fuel In the case of producing an integrated gel containing a liquid fuel for batteries, 0.01 to 50% by mass is preferable.

 [0089] In the present invention, a polymerization method for the carboxyl group and Z or sulfonic acid group-containing monomer, an cation substitution product of the monomer and, if necessary, another monomer (b) to be copolymerized is also a known method. For example, a solution polymerization method in a solvent in which each of the above monomers and the polymer to be formed dissolves, a bulk polymerization method in which polymerization is performed without using a solvent, and an emulsion polymerization method can be exemplified. Among these, the solution polymerization method is preferable.

[0090] The organic solvent by solution polymerization can be selected as appropriate depending on the solubility of the monomers and polymers used. For example, alcohols such as methanol and ethanol; carbonates such as ethylene carbonate, propylene carbonate and dimethyl carbonate; γ-butyrolacton Latatones such as _ε- strength prolatatum; ketones such as acetone and methyl ethyl ketone; carboxylic acid esters such as ethyl acetate; ethers such as tetrahydrofuran and dimethoxyethane; aroma such as toluene and xylene Group hydrocarbons and water. These solvents may be used alone or in combination of two or more.

 [0091] The polymerization concentration in the solution polymerization is not particularly limited and may vary depending on the intended use, but 1 to 80% by mass is preferable, and 5 to 60% by mass is more preferable.

 [0092] The polymerization initiator may be a conventional one. Azobis {2-methyl Ν— (2-hydroxyethyl) propionamide}, etc.], peracid-based initiators [peracid benzoyl, di-t-butyl peroxide, tamen hydroperoxide, succinic acid Peroxide, di (2-ethoxyethyl) peroxydicarbonate, hydrogen peroxide, etc.], redox initiator [combination of the above peroxide initiators and reducing agents (ascorbic acid or persulfate), etc.] Can be illustrated.

[0093] Examples of other polymerization methods include a method of adding a photosensitizer [benzophenone or the like] and irradiating ultraviolet rays or the like, a method of polymerizing by irradiating radiation such as y rays or electron beams, and the like. it can.

[0094] The amount of initiator added when a polymerization initiator is used is not particularly limited, but 0.0001 to 5% by mass is preferable with respect to the total mass of the monomers used. 2% by mass Is preferred.

 [0095] The polymerization temperature varies depending on the target molecular weight, the decomposition temperature of the initiator, the boiling point of the solvent used, and the like, but is preferably 20 to 200 ° C, more preferably 0 to 100 ° C.

 [0096] When the crosslinked product is in the form of particles, the volume average particle size is preferably 0.1 to 5000 µm, more preferably 50 to 2000 µm. Further, less than 0.1 m is preferably 10% by mass or less, and more than 5000 m is preferably 10% by mass or less, more preferably 5% by mass or less.

 [0097] The particle size was measured using a low-tap test sieve shaker and a JIS Z8801-2000 standard sieve. Perry's Chemical Engineers Handbook 6th edition (McGlow Hill Hill Book Company 1) 1984, p. 21) (hereinafter, this method is used to measure the particle size).

 [0098] 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 cross-linking agent and copolymerizing the polymer

A method of preparing the crosslinked product (A) of (1), distilling the solvent by a method such as drying, if necessary, and pulverizing it into a particulate form using a known pulverization method.

[Ii] (ii) Polymerization using a solvent, if necessary, to prepare a polymer (1), and then crosslinking the polymer (1) by means of the reactive crosslinking agent or radiation irradiation, etc. A method in which the solvent is distilled off by a method such as drying, if necessary, and pulverized using a known pulverization method to form particles.

 [oioo] (m) The above carboxyl group- and Z- or sulfonic acid group-containing monomer and, if necessary, another monomer (b) in the presence of the above-mentioned copolymerizable cross-linking agent, are copolymerized using a solvent as necessary to cross-link and After molecularization, the above-mentioned cation cation compound is added, the proton of the acidic group is replaced with a predetermined amount of cation, and then the solvent is distilled off by a method such as drying if necessary, and a known pulverization method is used. And pulverized into particles.

[0101] (iv) Uncrosslinked by copolymerizing the carboxyl group- and Z- or sulfonic acid group-containing monomer and optionally other monomer (b) in the absence of the copolymerizable crosslinking agent, if necessary, using a solvent. Then, the polymer is crosslinked at the same time as the proton of the acidic group is replaced by the addition of the onion cation compound and the reactive crosslinking agent or the irradiation of radiation. A method in which the solvent is distilled off by a method such as drying, if necessary, and pulverized using a known pulverization method to form particles.

 [0102] In the process of making the shape of the crosslinked body (A) of these fuel cell fuel stocks (hereinafter referred to as fuel stock! For example, aeration drying (air circulation dryer etc.), air permeation drying (band type dryer etc.), vacuum drying (vacuum dryer etc.), contact drying (drum dryer etc.) etc. can be mentioned.

 [0103] The drying temperature for drying is not particularly limited as long as the polymer or the like is not deteriorated or excessively cross-linked, but is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. . For example, impact pulverization (pin mill, cutter mill, ball mill type pulverizer, high-speed rotating type pulverizer such as ACM pulverizer, etc.), air pulverization, etc. can be used. (Jet pulverizer, etc.), freeze pulverization and the like.

 [0104] In this way, the 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.

 [0105] 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 a preferable form is a particulate form, a sheet form, or an integral form. Mention may be made of the form of gerui.

 [0106] A method of creating a preferred form will be described below, but the creation method and the like and the preferred method and the like differ slightly depending on the form.

 [0107] The particulate fuel reservoir may be one in which the particulate crosslinked body (A) has absorbed the fuel! /, And 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 volume average particle diameter and the like are preferably the same as those of the crosslinked product (A).

[0108] The particulate fuel composition has the ability to absorb 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 composition of the polymer, the gel strength, etc., and the crosslinked product (A) is converted into the fuel storage product. When used as, it is preferable to design the absorption amount to 10 to: LOOOgZg, more preferably 50 to 9 OOgZg. If the absorption amount is lOgZg or more, the liquid retention amount is significantly larger than that of conventional nonionic absorbents. If the absorption amount is lOOOgZg or less, the gel strength of the fuel stock holding liquid fuel is too weak! There is a problem!ヽ. [0109] Next, the case where the fuel composition is formed into a sheet shape will be described. Examples of the method for forming a sheet include the following methods (v) to (vii).

 [0110] (V) A method in which the particulate crosslinked product (A) is sandwiched between nonwoven fabrics, paper, or the like to form a sandwich sheet to absorb fuel.

 [0111] (vi) After impregnating and Z-coating a substrate made of one or more of nonwoven fabric, woven fabric, paper, and film with the uncrosslinked polymer (1), using the crosslinking agent The polymer (1) is cross-linked using one or two or more cross-linking means selected from the group consisting of cross-linking, cross-linking by radiation irradiation and cross-linking by heating, and the solvent is distilled off if necessary. After that, how to absorb the fuel.

[0112] (vii) 30~ 100 mole _^0/0 Proton the O of - substituted carboxyl group and Z or a sulfonic acid group-containing monomer 20 at Umukachion: and LOO wt%, the other copolymerizable mode Nomar After impregnating and Z or coating a substrate composed of one or two or more of nonwoven fabric, woven fabric, paper, and film with a mixed solution of 0 to 80% by mass of the crosslinking agent, the substrate Is polymerized using one or more cross-linking means selected from the group consisting of a polymerization initiator, cross-linking by irradiation with Z or radiation, and cross-linking by heating, and if necessary, the sheet is removed by distilling off the solvent. The method of absorbing the fuel after it is converted.

[0113] Among these methods, (vi) or (vii) is preferable from the viewpoints 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 1 to 50000 m force S, preferably 5 to 30000 m force S, more preferably 10 to 10000 m. If the sheet thickness is 1 m or more, the weight per unit area of the crosslinked product (A) will not be too small, and if it is 50000 μm or less, the sheet thickness will not be 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 LOm, 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 ability of the liquid fuel of interest and the ability to retain the liquid, and the thickness not becoming too thick. , Weight per unit area ί, 10 ~ 3000g / m ² force is preferred <, 20 ~: L000g / m ² force is more preferred! /, ₀

[0114] A base material such as a nonwoven fabric, a woven fabric, paper, or a film that is used as necessary to form the sheet may be a known material. For example, synthetic fibers having a basis weight of about 10 to 500 g and Z or ceiling However, examples include non-woven fabrics or woven fabrics made of fibers, paper (quality paper, thin paper, Japanese paper, etc.), films made of synthetic resins, and two or more substrates thereof and composites thereof.

 [0115] 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. is there.

 [0116] The thickness of these base materials is not particularly limited, but is usually 1 to 50000 111, preferably 10 to 20000 / ζ πι. If the thickness is less than 1 m, it is difficult to impregnate or apply the predetermined amount of the polymer (1). On the other hand, if the thickness exceeds 50000 m, the sheet is too thick to be used as a fuel storage. It becomes << to use when it becomes large. The coating method or impregnation method of the polymer (1) to the base material may be a well-known method. For example, after applying a coating or padding treatment, which may be performed by applying a method such as ordinary coating or padding, etc. The solvent used for polymerization, dilution, viscosity adjustment, etc. may be distilled off by a method such as drying, if necessary.

[0117] The sheet containing the cross-linked product (A) thus prepared absorbs fuel efficiently, and is therefore used as a sheet-type fuel storage. The amount of fuel absorbed in the seat-type fuel storage is not particularly limited as long as the fuel supply time is sufficiently long, but 0.1 to 50 Og—fuel Zcm ² —preferably l to 400 gZcm ² More preferred. If the absorbed amount is 0.1 lgZcm ² , the liquid fuel can be absorbed sufficiently, and if it is 500 gZcm ² or less, the sheet that has absorbed the liquid fuel is not too thick.

[0118] The ratio of the crosslinked body (A) Z fuel in the integral gelled fuel storage comprising the crosslinked body (A) and fuel is preferably 0.1 to 99Zl to 99.9% by mass, and preferably 0. 5~50Z50~99. 5 mass _^0/0, particularly preferably a 1~30Ζ70~99 mass _^0/0, most preferably from 1~20Ζ80~99 mass%. If the ratio of the cross-linked product (で) is 0.1% by mass or more, the resulting fuel-containing gel may not be able to gel the entire gel strength, while the content is 99% by mass or less. In this case, since the content of the crosslinked body (Α) is too large, the amount of fuel required is too low, and the discharge time of the battery is not shortened.

[0119] The same fuel as that described above can be used as the fuel used for the integral gel fuel storage. Examples of a method for preparing an integral gelled fuel storage include: (viii) a method of adding a predetermined amount of fuel to the above-mentioned particulate crosslinked body (A) of the present invention; (ix) the crosslinked body (A However, it is preferable that these fuel-containing gels can be used to form a gel that is integrated with the following methods (X) and (xi).

 [0120] (X) The polymer (1) is dissolved in a fuel, and the polymer (1) is cross-linked by any cross-linking means of cross-linking by the cross-linking agent, cross-linking by radiation irradiation, or cross-linking by heating. A method of forming a gel that is integrated by

[0121] (xi) in the fuel, the O - 30 to 100 mole _^0/0 protons substituted Cal Bokishiru group and Z or a sulfonic acid-containing monomer 20 at Umukachion: L00 wt%, and other co necessary A method in which 0 to 80% by mass of a polymerizable monomer is polymerized in the presence of the copolymerizable crosslinking agent to form an integrated gel.

 [0122] The form of the gel that also has a crosslinked body and fuel power can be selected as appropriate, and 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.

 [0123] The thickness of the gel in the case of a sheet-like gel is preferably 1 to 50000 111, more preferably 10 to 20000 μm. The width and length of the sheet-like gel may be appropriately selected according to the intended purpose, location, and usage.

 [0124] There are no particular limitations on the method of creating gels of these shapes, for example, prepared! /, A method of gelling in a container or cell that matches the shape, release paper, film, nonwoven fabric, etc. And a method of preparing a sheet-like gel by a method of laminating or coating a mixture of the polymer (1), the monomer, and the like and a liquid fuel.

[0125] The fuel composition may contain other gelling agents (fatty acid sarcophagus, dibenzal sorbite, hydroxypropyl cellulose, benzylidene sorbitol, carboxyvinyl polymer, polyethylene glycol, polyoxyanolylene, as necessary. Sonorebithonole, nitrocellulose, methinoresenorelose, ethinoresenorelose, acetinolebutinoresenellose, polyethylene, polypropylene, polystyrene, ABS resin, AB resin, acrylic resin, acetal resin, polycarbonate , Nylon, phenolic resin, phenoxy resin, urea resin, alkyd resin Fat, polyester, epoxy resin, diaryl phthalate resin, polyallomer, etc.), adsorbent (dextrin, dextran, silica gel, silica, alumina, molecular sieve, force orin, diatomaceous earth, carbon black, activated carbon, etc.), thickener In addition, one or two or more selected from the group consisting of a material force that can be converted into a non-fluidized state by chemically converting the binder and the fuel may be blended. These are not particularly limited as long as they can perform their respective functions, and they may be solid or liquid. Moreover, you may mix | blend in the arbitrary steps which produce a fuel store. Example

 [0126] Ability to describe the present invention more specifically with reference to the following examples. The present invention is not limited to the following examples unless it exceeds the gist of the present invention.

[Production Example 1]

 1,2—Bis (4 hydroxyphenol) cyclohexane (BHC) 26.8 g (0. lmol) was dissolved in 50 ml of methanol by heating and recrystallized to obtain BHC: methanol = 1: 1 ( A solid methanol clathrate compound having a methanol content of 11% by mass in a molar ratio) was obtained.

[Production Example 2]

 1, 1, 2, 2—Tetrakis (4 hydroxyphenol) ethane (THPE) 39.8 g (0. lmol) was dissolved in 100 ml of methanol by heating and recrystallized to obtain THPE: methanol = 1: 2 A solid methanol inclusion complex having a methanol content of 14% by mass (molar ratio) was obtained.

[Production Example 3]

360 g (5 mol) of acrylic acid, 1.08 g of pentaerythritol triallyl ether and 40 g of water 11 were placed in a 2 liter adiabatic polymerization tank. After cooling the monomer solution to 0 ° C and reducing the dissolved oxygen through nitrogen in the solution, 2, 2'-azobis (2 amidinopropane) hydride chloride as a polymerization initiator 0.36 g, 35% 3. 1 g of hydrogen peroxide and 0.38 g of L-scorbic acid were added to initiate the polymerization. After polymerization, the resulting hydrogel was subdivided using a meat chopper, and this gel was then subjected to 60% methanol of 1, 2, 3, 4-tetramethylimidazolium cation methyl carbonate (molecular weight: 203). -When 1353 g (4 mol) of a solution (Sanyo Kasei Co., Ltd.) was added, it was observed that decarboxylation and demethanol occurred. Using a band-type dryer (air-permeable dryer, manufactured by Inoue Kinzoku Co., Ltd.) to the gel to which the imidazolinium cation has been added, hot air at 100 ° C. is passed through, and water used as a solvent and By-product methanol was distilled off and dried. The obtained dried product is pulverized using a cutter mill to prepare a particulate crosslinked product having an average particle diameter of 400 m, and 100 g of this 20 g of methanol is absorbed to obtain a fuel composition (A1). It was.

[Examples 1 to 3]

 The methanol clathrate compound or fuel composition (A1) obtained in Production Examples 1 to 3 is filled in the fuel storage section 2 of the fuel cell fuel supply device 1 shown in FIG. When a sponge containing water was pressed into part 2 and water was inhaled, a methanol aqueous solution was generated even in the case of deviation, and this methanol aqueous solution was injected into the fuel cell test device.

The fuel cell was able to generate electricity.

[0131] Further, even if this fuel cell fuel supply device was dropped from the height of lm, no water leakage occurred, and the fuel cell could be similarly generated even when left at room temperature for 48 hours.

Claims

The scope of the claims

 [1] 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, characterized in that a liquid fuel component is caused to flow by the flow means so that the liquid fuel component can be supplied to the fuel cell.

 [2] The fuel storage portion stores a fuel composition for a fuel cell that is released by fuel cell fuel upon contact with water.

 The flow means is a moisture supply device;

 2. The aqueous solution of 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.

[3] The volume of the fuel storage section can be increased or decreased, and the fuel storage section is filled with microcapsules 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 to discharge the fuel cell fuel so that the fuel cell fuel can be supplied to the fuel cell. Fuel cell fuel supply device.

[4] The fuel storage portion can be increased or decreased in volume, and contains a fuel composition for a fuel cell that releases fuel for the fuel cell by contacting the fuel storage portion with water, and water. Filled with microcapsules,

 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, wherein

[5] The fuel supply device for a fuel cell according to any one of [1] to [4], wherein the fuel storage portion includes a liquid fuel absorber.

[6] The fuel for the fuel cell includes alcohols, ethers, hydrocarbons, and acetas. The fuel supply device for a fuel cell according to any one of claims 1 to 5, wherein the fuel supply device is one or more selected from the group consisting of