JP2007122895A - Fuel cell system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel cell system capable of carrying fuel for a fuel cell by filling a fuel composition in a cartridge, simply supplying fuel to a fuel cell cell, making the fuel cartridge compact and exchangeable, and using city water. <P>SOLUTION: The fuel cell system 1 is comprised of a fuel discharge mechanism 2 and the fuel cell cell 3, the fuel discharge mechanism 2 is equipped with the fuel cartridge 4, a water container 5, and a water supply mechanism 6 connecting the fuel cartridge 4 and the water container 5. The fuel cell cell 3 is fixed to the front of a frame body 7, and the fuel cartridge 4 and the water container 5 are detachably installed in the frame body 7. The water supply mechanism 6 is attached to the back surface of the frame body 7. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fuel cell system.

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, the direct methanol fuel cell fuel was used in liquid form, such as by impregnating and absorbing methanol in an absorbent material such as sponge, so there is a risk of liquid leakage during storage and transportation, which is highly dangerous. There are many problems above. 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. Further, the present applicants have previously proposed a method for releasing fuel cell fuel from those fuel cell fuels that are stable compositions (see Patent Document 4).
International Publication No. 2004/000857 Pamphlet JP 2004-127659 A Japanese Patent Laid-Open No. 8-231970 JP 2005-203335 A

  However, in the conventionally reported fuel release mechanism, water that passes through the container containing the fuel composition for the fuel cell exists as a liquid, and the water may leak. Therefore, it is conceivable to adopt a method of supplying a necessary amount of water using only the fuel composition as a cartridge as described in Patent Document 4, but there is still room for improvement in the specific structure. there were.

  In particular, when a fuel composition is used, water is indispensable for releasing the fuel in a liquid state. However, when both are made into a cartridge together, there is a problem that the cartridge becomes large.

  Furthermore, in order to make the fuel cell system versatile, it is desirable that the fuel cartridge is compact and that the cartridge can be replaced when the fuel is released, and that tap water can be used.

  The present invention has been made in view of the above problems, and by using the fuel composition as a cartridge, the fuel for the fuel cell can be safely carried and can be easily supplied to the fuel cell. The purpose is to provide a system. It is another object of the present invention to provide a fuel cell system in which the fuel cartridge is compact and replaceable and can use tap water.

  The fuel cell system of the present invention is a fuel cell system comprising a fuel release mechanism and a fuel cell arranged close to the fuel release mechanism, wherein the fuel release mechanism is a fuel in which a liquid fuel component is solidified. A fuel cartridge that expropriates the composition; a water container provided in proximity to the fuel cartridge; and a water supply mechanism that connects the water container and the fuel cartridge, the fuel cell, the fuel cartridge, and the water container Are integrally assembled, and the fuel cartridge is detachably provided (Claim 1).

  According to the above invention (invention 1), since the liquid fuel component is solidified, it can be carried and stored, and further, the water container and the fuel cartridge are connected by the water supply mechanism, and the fuel cartridge is connected from the water container. By supplying water to the liquid fuel component, the liquid fuel component is released, and the fuel is supplied to the fuel battery cell to generate power. Moreover, since the water container and the fuel cartridge are separately provided, the fuel cartridge can be made compact, and only the fuel cartridge can be replaced.

  In the above invention (invention 1), the fuel cartridge has a water injection port formed on the upper side and a fuel supply port formed on the bottom surface portion, and the fuel cell unit is close to the fuel supply port. Is preferably arranged (claim 2). By adopting such a configuration, the fuel can be easily supplied to the fuel battery cell.

  In the above inventions (Inventions 1 and 2), it is preferable that a water supply port is formed in the water tank, and an ion exchanger is provided close to the water supply port (Invention 3), In the above inventions (inventions 2 and 3), the fuel cartridge preferably has a structure in which an ion exchanger, an elastic water absorbing member, and a fuel composition are sequentially laminated from the water inlet side (invention 4). ). Thereby, tap water permeates the ion exchanger, so that ionic impurities are removed and high-purity water can be supplied to the fuel cartridge, and power generation efficiency is improved in the generation of electricity in the fuel cell. be able to.

  In the above inventions (inventions 1 to 4), the water supply mechanism connects the pump device, the first connection pipe connecting the pump device and the water container, and the pump device and the fuel cartridge. (Claim 5), and the water supply mechanism preferably further includes a drainage function (Claim 6). By adopting such a configuration, water can be reliably supplied to the fuel cartridge, and fuel can be recirculated when use is stopped.

  According to the fuel cell system of the present invention having the above-described configuration, the liquid component can be absent in the fuel cartridge during storage (claim 7).

  As the liquid fuel component, one or more selected from the group consisting of alcohols, ethers, hydrocarbons, and acetals can be used (claim 8). The fuel cell system of the present invention is characterized in that the fuel composition includes a molecular compound of a liquid fuel component and a counterpart compound (claim 9). The molecular compound of the fuel composition is an inclusion compound formed from the fuel for a fuel cell and a host compound (claim 10). Moreover, what contains the fatty acid ester of a polyhydric alcohol and the fuel for fuel cells as said fuel composition can also be used (Claim 11).

  In the fuel cell system of the present invention, since the fuel composition obtained by solidifying the liquid fuel component is put into the case as a fuel cartridge, the liquid fuel component can be solidified and stored. Further, the water container, the fuel cartridge, Are separately provided, the fuel cartridge can be made compact, and only the fuel cartridge can be replaced.

Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a perspective view showing a fuel cell system according to an embodiment of the present invention, FIGS. 2 and 3 are exploded perspective views thereof, and FIG. 4 is a fuel cell according to an embodiment of the present invention. FIG. 5 is an exploded perspective view showing a water container in the system, and FIG. 5 is an exploded perspective view showing a fuel cartridge in the fuel cell system according to one embodiment of the present invention.

  1 to 3, the fuel cell system 1 includes a fuel release mechanism 2 and a fuel cell 3, and the fuel release mechanism 2 includes a fuel cartridge 4, a water container 5, the fuel cartridge 4 and water. A water supply mechanism 6 for connecting the container 5 is provided. The fuel cell 3 is fixed to the front surface of the frame body 7, and the fuel cartridge 4 and the water container 5 are detachably provided. On the other hand, a water supply mechanism 6 is attached to the back side of the frame body 7.

  As shown in FIG. 3, the water supply mechanism 6 includes first connection pipes 8 and 8 A connected to the water container 5, a pump device 9, and a second connection pipe 10 connected to the fuel cartridge 4. The first connection pipe line 8A and the second connection pipe line 10 are connected to the pump device 9, respectively. Reference numeral 11 denotes a drainage connection pipe, and the drainage connection pipe 11 can be switched to the first connection pipe 8 by a three-way valve 12 so that the drainage function can be exhibited. Yes. In addition, 12A is a three-way valve switching lever, 13 is an exhaust pipe line, 14 is a cover of the water supply mechanism 6, and 15 is a cover of the fuel cartridge 4.

  In the fuel cell system 1 as described above, as shown in FIG. 4, the water container 5 includes a container main body 21 and a water supply connector 22 connected to the first connection pipe 8 provided on the side surface of the container main body 21. A drainage connector 23 connected to the drainage connection pipe line 11, an exhaust connector 24 connected to the exhaust pipe line 13, and a cover member 25. The cover member 25 is provided with a lid 26 as a water inlet, and water can be supplied by opening and closing the cap 27. Further, a packing 28 is provided between the cover member 25 and the container main body 21, and further, an ion exchange fiber 29 as an ion exchanger and a pedestal 30 on which the ion exchange fiber 29 is placed Is provided.

  Further, as shown in FIG. 5, the fuel cartridge 4 is a casing body 31, a net body 32, ion-exchange fibers 33 that are ion exchangers, and an elastic water-absorbing body housed in the casing body 31. It has a sponge 34, a water-permeable fuel storage case 35 that stores a methanol clathrate compound that is a fuel composition, and a net 36. On the upper side of the ion exchange fiber 33, a water inlet (not shown) communicating with the second connection pipe line 10 is formed. A pressing member 37 having an opening 37 </ b> A as a fuel supply port is attached to the lower side of the net body 36, and communicates with the fuel cell 3 from the opening 37 </ b> A. Reference numerals 38, 38... Are compression coil springs, and the pressing member 37 is always urged downward by the compression coil springs 38. The fuel cartridge 4 can be inserted and removed by having such a configuration. That is, by compressing the compression coil spring 38 and reducing the height, the compression coil spring 38 can be inserted into the space formed by the frame body 7 and the cover 15, and after the insertion, the compression coil spring 38 is stretched by elastic force. The fuel cartridge 4 is held in the space. Further, by pulling the fuel cartridge 4 at a predetermined load or more, the compression coil spring 38 can be contracted and extracted.

  On the other hand, the fuel cell 3 includes a current collector plate 41 made of a mesh member on the fuel electrode side fixed to the metal plate 41A, a current collector plate (not shown) made of a mesh member on the air electrode side, and a space between them. MEA (membrane electrode assembly) 42 provided in The MEA 42 is a thin plate member in which a fuel electrode, an electrolyte membrane, and an air electrode are integrally laminated, and each of the fuel electrode and the air electrode is brought into contact with a current collector plate to take out electrons. For this reason, conductive plates 43 and 44 for connecting wires to an electric device or the like are connected to the metal plate 41A on the fuel electrode side and the current collector plate of the air electrode, respectively.

  The effect | action is demonstrated about the said structure. First, the cap 27 of the water container 5 is removed, tap water is supplied from the lid 26, and water is stored in the container body 21. At this time, the tap water passes through the ion-exchange fiber 29 to remove ionic impurities and become high-purity water.

And if the pump apparatus 9 is started in the state which made the three-way valve 12 the 1st connection pipe line 8 side, water will be attracted | sucked from the water supply connector 22 attached to the side part lower part of the water container 5, and it is shown as the continuous line in FIG. As shown by the arrows, the water inlet of the fuel cell cartridge 4 (not shown) from the first connection pipe 8, the three-way valve 12, and the first connection pipe 8A through the pump device 9 and from the second connection pipe 10 is shown. )). Then, this water passes through the ion exchange fiber 33 in the fuel cell cartridge 4 to become higher-purity water, reaches the fuel storage case 35 from the sponge 34, and comes into contact with the methanol clathrate compound in the fuel storage case 35. As a result, methanol is released, and a fuel cell fuel composed of an aqueous methanol solution is produced. The methanol aqueous solution that is the fuel solution for the fuel cell passes through the mesh body of the current collector plate 41 from the opening 37A of the holding member 37, and is smoothly supplied to the MEA 42 of the fuel cell 3, and the fuel electrode catalyst of the MEA 42 Depending on the component, it is converted into hydrogen ions (H ⁺ ), carbon dioxide (CO ₂ ), and electrons (e ⁻ ). The electrons (e ⁻ ) are electrically connected, and the hydrogen ions (H ⁺ ) pass through the MEA 42. , Respectively, are introduced into the air electrode of the MEA 42. On the other hand, air or oxygen (O ₂ ) is supplied at the air electrode, and this oxygen (O ₂ ) reacts with hydrogen ions (H ⁺ ) and electrons (e ⁻ ) generated at the fuel electrode to produce water. In such a reaction, by connecting the conductive plates 43 and 44 to the wiring of the electric device, a circuit is formed via the fuel electrode side current collecting plate 41 and the air electrode side current collecting plate (not shown), and the electric power is generated. It is taken out.

  And when stopping supply of electric power, the lever 12A is switched, the three-way valve 12 is switched to the drainage connecting pipe line 11 side, and the pump device 9 is operated in the reverse rotation state. As indicated by an arrow, a methanol aqueous solution is sucked from the second connection pipe 10, and the container is discharged from the drainage connector 23 through the pump device 9, the first connection pipe 8 </ b> A, the three-way valve 12 and the drainage connection pipe 11. Return to the main body 21. At this time, the sponge 34 absorbs the excess methanol aqueous solution in the fuel cartridge 4, so that the methanol aqueous solution does not leak.

  Thus, in this embodiment, since the fuel cartridge 4 storing methanol as a fuel does not contain water, it can be safely stored and transported, and the water container 5 is filled with water during use. The methanol aqueous solution as the fuel can be supplied to the fuel cell 3 simply by pushing the fuel cartridge 4 in the state and starting the pump device 9. In addition, since the water supply mechanism 6 has a function of draining the methanol aqueous solution in the fuel cartridge 4 as in the present embodiment, there is no risk of leakage of the methanol aqueous solution, and the state is a dilute methanol aqueous solution. There is also an effect that the above safety problem can be solved. Furthermore, since the fuel cartridge 4 and the water container 5 can be stored separately, the fuel cartridge 4 can be made compact. Moreover, it is possible to replace only the fuel cartridge 4, and the water container 5 can be used for a long period of time simply by replenishing tap water.

  In the present embodiment, the ion exchange fibers 29 and 33 are provided in both the fuel cartridge 4 and the water container 5, but it is not always necessary to provide both, and either one may be provided.

  In the present embodiment as described above, the case where a methanol clathrate compound is used as the fuel composition has been described as an example, but the following can also be used as the fuel composition. That is, examples of the fuel for fuel cells (or liquid fuel components) include alcohols such as methanol, ethers, hydrocarbons, or acetals, which can be used as fuel for solid polymer fuel cells. However, the present invention is not limited to these. Specifically, hydrogen; alcohols such as 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, trime Examples include acetals such as toschimethane, but are not limited thereto, and these may be used alone or in combination of two or more.

  The fuel cell is preferably a polymer electrolyte fuel cell. Among them, a direct methanol fuel cell is suitable as in the above embodiment, 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 of the 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 includes 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 is changed to a solid compound, so that the fuel is relatively light and stable. Battery fuel 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, bixanthenes , Carboxylic acids, imidazoles, hydroquinones and the like.

Polymeric hosts include celluloses, starches, chitins, chitosans, polyvinyl alcohols, polyethylene glycol arm polymers with 1,1,2,2-tetrakisphenylethane as the core, α, α, α And polyethylene glycol arm type polymers having ', α'-tetrakisphenylxylene as a core.
In addition, organophosphorus compounds, organosilicon compounds, and the like are also included.

  Examples of inorganic host compounds include titanium oxide, graphite, alumina, transition metal dicargogenite, lanthanum fluoride, clay minerals (such as montmorillonite), silver salts, silicates, phosphates, zeolites, silica, and porous glass. 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. Further, 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.
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'-dihydroxybenzophenone, 2,2 ' 4,4′-tetrahydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-sulfonylbisphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4, 4′-ethylidenebisphenol, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-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-hydroxy) Phenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, α, α, α ′, α′-tetrakis (4-H Droxyphenyl) -p-xylene, 3,6,3 ′, 6′-tetramethoxy-9,9′-bi-9H-xanthene, 3,6,3 ′, 6′-tetraacetoxy-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) ) Hydroquinone and the like, and phenolic host compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane are advantageous in terms of easy industrial use.

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

  Furthermore, 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. As a method for producing such an organic / inorganic composite material, the above-mentioned organic host compound is dissolved in a solvent capable of dissolving, the solution is impregnated in an inorganic porous material, and the solvent is dried, dried under reduced pressure, or the like. Can be manufactured. 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.

  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, the fuel cell fuel and the host compound are directly contacted and mixed. Thus, it can be easily synthesized, and it can also be obtained by heating and the like to dissolve the host compound in the fuel for the fuel cell and recrystallizing it. Further, when the fuel for the fuel cell is a gas or liquid, it can be obtained by bringing the fuel into contact 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., but usually 0.1 to 10 fuel molecules for the fuel cell per mole of the host compound. It is an clathrate compound that clathrates a mole.

  This clathrate compound can stably store fuel for fuel cells over a long period of time in a normal temperature / normal pressure environment. Moreover, since this inclusion compound is lightweight and excellent in handleability and is solid, it can be easily stored in a container such as glass, metal, plastic, etc., 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.

  In addition to this, 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 Alternatively, 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 the sulfonic acid group are substituted with an onium cation and a fuel for a fuel cell is also used. Can do. 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, malein Acid, itaconic acid, fumaric acid, cinnamic acid, and their anhydrides]; monomers having a sulfonic acid group [eg, aliphatic vinyl sulfonic acid [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 [[acrylamide-2-methylpropanesulfonic acid etc.] etc. One or more of these are the structural units in the polymer (1) It is possible. 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 structural units having sulfonic acid groups introduced into the molecule, carboxyl groups represented by carboxymethyl cellulose, polysaccharide polymers containing sulfonic acid groups, and graft copolymers of the polysaccharide polymers and other monomers In the end, a polymer containing a predetermined amount of a structural unit having a carboxyl group and / or a sulfonic acid group is obtained. As long as it is not particularly limited.

  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%. If the content is less than 20% by mass, the amount of absorption with respect to the liquid fuel of interest will decrease even if the proton of a carboxyl group or sulfonic acid group is replaced with an onium cation described later, or the liquid fuel can be gelled with a small amount. There may be no.

Examples of the copolymerizable monomer (b) forming a structural unit other than the structural unit having a carboxyl group and / or a sulfonic acid group include, for example, (meth) alkyl acrylate (C1-30) esters [(meth) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethyl hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Stearyl acid, phenyl (meth) acrylate, octylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.]; (meth) acrylic acid oxyalkyl (1 to 4 carbon atoms) [hydroxyethyl (meth) acrylate , (Meth) acrylic acid hydroxypropyl, (meth) acrylic acid mono (polyethylene group) Cole) 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 Ter, 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 (alkyl carbon number: 1 to 5) aminoethyl (meth) acrylate, meth (acryloyl) oxyethyltrialkyl (alkyl carbon number: 1 to 5) ammonium chloride, bromide, sulfate, etc.] and the carboxyl group, sulfonic acid An alkali metal salt of a monomer having a group,
Examples thereof include primary to tertiary amine salts or alkanolamine salts. 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.

  As the monomer (b), (meth) acrylic acid alkyl esters, oxyalkyl (meth) acrylates, allyl ethers, α-olefins, from the viewpoint of the polymerizability of the monomer and the stability of the produced polymer, etc. It is preferable to use aromatic vinyl compounds.

  The monomer (b) whose difference between the SP value of the solvent and the SP value of the monomer (b) is 5 or less is selected in accordance with the SP value (solubility parameter) of the solvent to be absorbed or gelled by the liquid fuel. This is preferable because the absorption amount and gelling power are likely to increase, and it is more preferable to select one having a difference between the SP value of the target solvent and the SP value of the monomer (b) of 3 or less.

  It is desirable to replace the proton of the carboxyl group and / or the sulfonic acid group by 30 to 100 mol% with an onium cation. The onium cation is selected from the group of cations consisting of a quaternary ammonium cation (I), a tertiary sulfonium cation (II), a quaternary phosphonium cation (III), and a tertiary oxonium cation (IV). Species or two or more can be used. 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-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl -2H-pyrimido [1,2a] imidazolinium, 2-dimethylamino-3-methylcarboxymethyl-1-methylimidazo 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-dimethyl Amino-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-dimethylphosphonium, 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) 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 individually by 1 type, and may use 2 or more types together.

  Examples of the method for introducing the onium cation into the polymer include a method in which the proton of the carboxyl group and / or the sulfonic acid group of the polymer is substituted with the onium cation. The method for substituting a proton with an onium cation is not particularly limited as long as it is a method capable of substituting a predetermined amount of onium cation. For example, the above onium cation hydroxide salt (for example, tetraethylammonium hydroxide) or monomethyl carbonate is used. Compound salt (for example, 1,2,3,4-tetramethylimidazolinium monomethyl carbonate, etc.) is added to a polymer containing a carboxyl group and / or a sulfonic acid group, and if necessary, dehydration, decarboxylation, demethanolysis -Can be easily replaced by carrying out 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 a sulfonic acid group is substituted with an onium cation, or a polymer having a carboxyl group and / or a sulfonic acid group (1 ), After the proton of the acid is replaced with an onium cation, the proton of the carboxyl group and / or the sulfonic acid group of the polymer (1) is finally replaced. It may be performed at any stage.

  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 lowered.

  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] Cross-linking with a copolymerizable cross-linking agent;
Copolymerizable with the carboxyl group and / or sulfonic acid group-containing monomer, an onium cation-substituted product of the monomer, and, if necessary, other monomer (b) to be copolymerized or having two or more double bonds in the molecule Crosslinker [polyvalent vinyl type crosslinker such as divinylbenzene, (meth) acrylamide type crosslinker such as N, N′-methylenebisacrylamide, polyvalent allyl ether type crosslinker such as pentaerythritol triallyl ether, trimethylol A method of copolymerizing and crosslinking a polyvalent (meth) acrylic acid ester type crosslinking agent such as propane triacrylate].

[2] Cross-linking with a reactive cross-linking agent;
Reactive crosslinking agent [4,4′-diphenylmethane having in the molecule two or more functional groups capable of reacting 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 Polyisocyanate type cross-linking agent such as diisocyanate, polyhydric epoxy type cross-linking agent such as polyglycerol polyglycidyl ether, polyhydric alcohol type cross-linking agent such as glycerol, polyvalent amine such as hexamethylenetetramine and polyethyleneimine, imine type cross-linking agent , A haloepoxy type crosslinking agent such as epichlorohydrin, a polyvalent metal salt type crosslinking agent such as aluminum sulfate, etc.].

[3] Crosslinking with a polymerization reactive crosslinking agent;
The carboxyl group and / or sulfonic acid group-containing monomer, an onium cation-substituted product of the monomer, copolymerizable with another monomer (b) to be copolymerized if necessary, or having a double bond in the molecule, and a carboxyl group And / or a sulfonic acid group or an onium cation-substituted product thereof, and a polymerization reactive crosslinking agent having a functional group capable of reacting with a functional group of a monomer to be copolymerized if necessary [glycidyl (meth) acrylate type such as glycidyl methacrylate] Crosslinking using a crosslinking agent, an allyl epoxy type crosslinking agent such as allyl glycidyl ether, etc.].

[4] Cross-linking by irradiation;
A method of crosslinking the polymer (1) by irradiating the polymer (1) with radiation such as ultraviolet rays, electron beams, γ rays, or the like, and simultaneously polymerizing and crosslinking by irradiating the monomers with ultraviolet rays, electron beams, γ rays, etc. How to do etc.

[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) [crosslinking between carbons due to generation of radicals by heating or crosslinking between functional groups].

  Among these crosslinking methods, the preferred ones vary depending on the use and form of the final product, but when considered comprehensively, [1] crosslinking with a copolymer crosslinking agent, [2] crosslinking with a reactive crosslinking agent, and [4] radiation. Cross-linking by 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 weight. 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 carboxyl group and / or sulfonic acid group-containing monomer, the onium cation-substituted product of the monomer, and the other monomer (b) to be copolymerized if 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 appropriately selected depending on the solubility of the monomer and polymer used. Examples thereof include alcohols such as methanol and ethanol; carbonates such as ethylene carbonate, propylene carbonate and dimethyl carbonate; γ-butyrolactone, ε- Examples include lactones such as 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. . 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, and 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.], redox initiator [a combination of the above peroxide-based initiator and a reducing agent (ascorbic acid or persulfate), etc.], and the like. .

  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 using a low-tap test sieve shaker and JIS Z8801-2000 standard sieve, Perry's Chemical Engineers Handbook, 6th edition (McGlow Hill Book Company, 1984, p. 21). (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, the copolymerizable crosslinking agent is copolymerized to prepare a crosslinked body (A) of the polymer (1), and if necessary, the solvent is distilled off by a method such as drying. A method of pulverizing into particles using the above pulverization method.

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

(Iii) After the carboxyl group and / or sulfonic acid group-containing monomer and, if necessary, other monomer (b) are copolymerized using a solvent in the presence of the copolymerizable cross-linking agent and cross-linked to form a polymer. The onium cation compound is added, and the proton of the acid group is replaced with a predetermined amount of onium cation, and then the solvent is distilled off by a method such as drying if necessary, followed by pulverization using a known pulverization method to form particles. Method.

(Iv) The carboxyl group and / or sulfonic acid group-containing monomer and, if necessary, the other monomer (b) are copolymerized using a solvent if necessary in the absence of the copolymerizable crosslinking agent to obtain an uncrosslinked polymer. Thereafter, the onium cation compound and the reactive cross-linking agent and radiation irradiation are used to simultaneously replace the proton of the acid group to cross-link the polymer, and if necessary, the solvent is distilled off by a method such as drying. A method of pulverizing into particles by using a pulverization method.

  The drying performed as necessary in the process of making the shape of the crosslinked body (A) of the fuel cell fuel storage (hereinafter referred to as fuel storage) into particles may be a known drying method, for example, ventilation drying (circulation drying). Etc.), air permeation drying (such as a band-type dryer), vacuum drying (such as a vacuum dryer), contact drying (such as a drum dryer), and the like.

  The drying temperature in the case of 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. 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), air pulverization (jet pulverization) And the like, and freeze grinding.

  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 is made into particles in this way has the ability to absorb fuel.

  The fuel composition accommodated in the fuel cell system of the present invention can be processed into various forms, and the form is not particularly limited, but is preferably in the form of particles, sheets, and integral gelation.

  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 has the ability to absorb fuel. The amount of the crosslinked body (A) absorbed in the fuel storage according to the present invention varies depending on the type of the target fuel, the polymer composition, the gel strength, etc., and the (A) is used as the fuel storage. In this case, it is preferable to design the amount of absorption with respect to methanol to 10 to 1000 g / g, and more preferably to 50 to 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 one or more substrates selected from the group consisting of nonwoven fabric, woven fabric, paper and film with the uncrosslinked body of the polymer (1), After cross-linking the polymer (1) 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 if necessary, after distilling off the solvent and forming a sheet, A method of absorbing fuel.

(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 one or more substrates selected from the group consisting of nonwoven fabrics, woven fabrics, papers and films with the mixed solution composed of the agent, the substrate is polymerized with a polymerization initiator and / or radiation, etc. A method of polymerizing by using one 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) and the absorption rate of the prepared sheet. 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 length and width of the sheet 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 that is used as necessary to form the sheet may be a known one. For example, a nonwoven fabric made of synthetic fibers or natural fibers having a basis weight of about 10 to 500 g. Or a woven fabric, paper (quality paper, thin paper, Japanese paper, etc.), a film made of a synthetic resin, two or more substrates thereof, or 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 about 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). On the other hand, when the thickness exceeds 50000 μm, the sheet is too thick and the overall bulk is large when used as a fuel storage. 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 method such as coating or padding may be applied. In addition, after performing a coating or padding process, you may distill away the solvent used for superposition | polymerization, dilution, viscosity adjustment, etc. by drying etc. as needed.

The sheet containing the cross-linked product (A) thus prepared absorbs fuel efficiently and is used as a sheet-type fuel storage. Absorption for the fuel in the sheet-type fuel reservoir also the supply time of the fuel is not particularly limited as longer enough, preferably 0.1 to 500 g / cm ² sheets further those 1~400g / cm ² preferable. When the absorption amount is 0.1 g / cm ² or more, 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 (A) is 0.1% by mass or more, the produced fuel-containing gel has a weak gel strength, and there is no case where the entire gel cannot be gelled. On the other hand, when the content is 99% by mass or less, Since the content of (A) is too large, the required amount of fuel added is not too low and the discharge time of the 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 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) containing (A) However, it is preferable that these fuel-containing gels can produce an integrated gel by the methods described in (x) and (xi) below.

(X) The polymer (1) is dissolved in a fuel, and the (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 cross-linking 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 of creating the gel of these shapes, for example, the method of gelling in a container or cell that matches the shape to be created, release paper, film, nonwoven fabric, etc. Examples thereof include a method of preparing a sheet-like gel by laminating or coating a mixture of the polymer (1), the monomer, and the like and a liquid fuel.

  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, and a binder, and fuel may be blended with one or more 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.

[Example 1]
In the fuel cell system 1 shown in FIGS. 1 to 5, the fuel cartridge 4 is filled with the methanol clathrate compound 15 g obtained in Production Example 1 and the beads 95 g, and the tap water is supplied to the water container 5 to supply the pump device. When No. 9 was operated and water was allowed to flow into the fuel cartridge 4, an aqueous methanol solution was produced. Electric power could be generated by supplying the methanol aqueous solution to the fuel cell 3. Next, when the three-way valve 12 was switched to the discharge side and the pump device 9 was reversed, power generation was stopped, and the aqueous methanol solution remaining in the fuel cartridge 4 could be recovered in the water container 5. It was confirmed that power generation / stop can be reproduced by repeating this operation.

1 is a perspective view schematically showing a fuel cell system according to an embodiment of the present invention. 1 is an exploded perspective view showing a fuel cell system according to an embodiment of the present invention. It is a disassembled perspective view from the back side of the fuel cell system concerning one embodiment of the present invention. It is a disassembled perspective view which shows the water container in the fuel cell system which concerns on one Embodiment of this invention. 1 is an exploded perspective view showing a fuel cartridge in a fuel cell system according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Fuel cell system 2 ... Fuel discharge | release mechanism 3 ... Fuel cell 4 ... Fuel cartridge 5 ... Water container 6 ... Water supply mechanism 7 ... Frame main body 8, 8A ... 1st connection pipe line 9 ... Pump apparatus 10 ... 2nd Connection pipe line 26 ... Lid (water supply port)
29 ... Ion exchange fiber (ion exchanger)
33 ... Ion exchange fiber (ion exchanger)
34 ... Sponge (elastic water absorber)
37A ... Opening (fuel supply port)

Claims (11)

A fuel cell system comprising a fuel release mechanism and a fuel cell arranged close to the fuel release mechanism,
A fuel cartridge that uses a fuel composition obtained by solidifying a liquid fuel component; a water container provided close to the fuel cartridge; and a water supply mechanism that connects the water container and the fuel cartridge. With
The fuel cell system, wherein the fuel cell, the fuel cartridge, and the water container are integrally assembled, and the fuel cartridge is detachably provided.   The fuel cartridge has a water injection port formed on the upper side, a fuel supply port formed on the bottom surface portion, and the fuel cell is disposed in the vicinity of the fuel supply port. The fuel cell system according to claim 1.   The fuel cell system according to claim 1, wherein a water supply port is formed in the water tank, and an ion exchanger is provided adjacent to the water supply port.   4. The fuel cell system according to claim 2, wherein the fuel cartridge has a structure in which an ion exchanger, an elastic water absorbing member, and a fuel composition are sequentially stacked from a water inlet side. 5.   The water supply mechanism includes a pump device, a first connection pipe that connects the pump device and the water container, and a second connection pipe that connects the pump device and the fuel cartridge. The fuel cell system according to any one of claims 1 to 4, characterized in that:   The fuel cell system according to claim 1, wherein the water supply mechanism further includes a drainage function.   The fuel cell system according to claim 1, wherein no liquid component is present in the initial fuel cartridge.   The fuel according to any one of claims 1 to 7, wherein the liquid fuel component is one or more selected from the group consisting of alcohols, ethers, hydrocarbons, and acetals. Battery system.   The fuel cell system according to any one of claims 1 to 8, wherein the fuel composition contains a molecular compound of a liquid fuel component and a counterpart compound.   10. The fuel cell system according to claim 9, wherein the molecular compound of the fuel composition is an inclusion compound formed from the fuel for a fuel cell and a host compound. The fuel cell system according to any one of claims 1 to 8, wherein the fuel composition contains a fatty acid ester of a polyhydric alcohol and a fuel for a fuel cell.

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