WO2019043977A1 - Matériau d'absorption d'humidité - Google Patents

Matériau d'absorption d'humidité Download PDF

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WO2019043977A1
WO2019043977A1 PCT/JP2018/001652 JP2018001652W WO2019043977A1 WO 2019043977 A1 WO2019043977 A1 WO 2019043977A1 JP 2018001652 W JP2018001652 W JP 2018001652W WO 2019043977 A1 WO2019043977 A1 WO 2019043977A1
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polymer
hygroscopic
stimulus
ligand
responsive
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PCT/JP2018/001652
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English (en)
Japanese (ja)
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伸基 崎川
隆志 宮田
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シャープ株式会社
学校法人関西大学
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Priority to CN201880052362.1A priority Critical patent/CN111050883A/zh
Priority to JP2019538929A priority patent/JP7460066B2/ja
Publication of WO2019043977A1 publication Critical patent/WO2019043977A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds

Definitions

  • the present invention relates to a hygroscopic material.
  • deliquescent inorganic salts such as calcium chloride, magnesium chloride and aluminum chloride are used as hygroscopic materials.
  • the deliquescent inorganic salt is excellent in hygroscopicity, it tends to liquefy after absorbing moisture, and there is a problem that the liquid leaks out and contaminates the surroundings.
  • a desiccant (refer to Patent Document 1) containing a deliquescent inorganic salt and a non-ionic cellulose derivative as a gelling agent, a dehumidifying material comprising deliquescent inorganic salts, a hydrophilic polymer and cellulose powder A composition (see Patent Document 2) and the like are known.
  • Japanese Patent Publication Japanese Patent Application Laid-Open No. 201-194497
  • Japanese Patent Publication Japanese Patent Application Laid-Open No. 2000-5553
  • the present invention has been made in view of the above problems, and an object thereof is to realize a hygroscopic material excellent in hygroscopicity while preventing leakage of deliquescent liquid when it contains a deliquescent inorganic salt. .
  • a hygroscopic material according to an embodiment of the present invention is a hygroscopic material containing a hygroscopic polymer material, and the hygroscopic polymer material contains a hydrophilic polymer, in order to solve the problems.
  • the hygroscopic polymer material is characterized in that a ligand having an affinity to a monovalent, divalent or trivalent metal ion is bound.
  • the hygroscopic material according to one embodiment of the present invention is a hygroscopic material containing a hygroscopic polymer material as described above, wherein the hygroscopic polymer material contains a hydrophilic polymer, and the hygroscopic material is Since the polymer material has a configuration in which a ligand having an affinity to a monovalent, divalent or trivalent metal ion is bound, it is possible to capture a salt of the metal ion having high hygroscopicity. While preventing the leakage of the deliquescent solution derived from the said salt, it is effective in the ability to implement
  • Embodiment 1 Hygroscopic Material
  • the present inventors contain a hydrophilic polymer, and the hygroscopic polymer material is a ligand having an affinity for a monovalent, divalent or trivalent metal ion.
  • the bound hygroscopic material can capture the salt of the metal ion having high hygroscopicity, and can prevent leakage of the deliquescent solution derived from the salt, and can realize a hygroscopic material superior in hygroscopicity.
  • the present invention has been completed.
  • the hygroscopic material according to one embodiment of the present invention is a hygroscopic material containing a hygroscopic polymeric material, and the hygroscopic polymeric material contains a hydrophilic polymer, and the hygroscopic polymeric material And a ligand having an affinity to a monovalent, divalent or trivalent metal ion.
  • a hygroscopic material contains a hygroscopic polymer material, and a ligand having an affinity for a monovalent, divalent or trivalent metal ion is bound to the hygroscopic polymer material. ing.
  • the ligand has an affinity for monovalent, divalent or trivalent metal ions, and thus can capture monovalent, divalent or trivalent metal ions. Therefore, salts of the metal ions having high hygroscopicity can be captured by the hygroscopic polymeric material, and hygroscopicity of the hygroscopic polymeric material can be enhanced.
  • a conventional moisture absorbent containing a deliquescent inorganic salt and a polymer as a gelling agent is a mixture of a deliquescent inorganic salt and a polymer as a gelling agent.
  • the moisture absorbent according to an embodiment of the present invention has higher moisture absorption. The reason is that since the ligand can be uniformly dispersed in the hygroscopic polymer material, the salt of the metal ion can be dispersed more uniformly, which enables more efficient moisture absorption. It is believed that there is.
  • binding in the description of “ligand is binding” is not limited to this, but, for example, via chemical bond such as covalent bond, ionic bond, coordination bond, etc. It is preferable that it is couple
  • the ligand is stably immobilized in the hygroscopic polymeric material. More specifically, the ligand can be suitably bonded to the hygroscopic polymeric material by introducing a reactive functional group into the ligand and reacting the reactive functional group with the hygroscopic polymeric material. .
  • bonded with the hygroscopic polymeric material should just be couple
  • (I) Ligands Having Affinity for Monovalent, Divalent, or Trivalent Metal Ions examples include Li + , Na + , K + , Rb + , Cs + and the like.
  • the monovalent metal ions include Li + , Na + , K + , Rb + , Cs + and the like.
  • Mg ⁇ 2+> , Ca ⁇ 2+> , Sr ⁇ 2+> , Ba ⁇ 2+> etc. can be mentioned, for example.
  • As said trivalent metal ion, Al ⁇ 3+> , Y ⁇ 3+> , In ⁇ 3+> , Sc ⁇ 3+> , a lanthanoid ion group etc. can be mentioned, for example.
  • the ligand is preferably a host molecule that forms a clathrate, a chelating agent, or a molecule having a functional group that forms an ionic bond with the metal ion.
  • the host molecule includes a metal ion, the chelating agent coordinates the metal ion, and the molecule having a functional group which forms an ionic bond with the metal ion forms an ionic bond with the metal ion. It can capture ions.
  • the host molecule is selected from the group consisting of cyclodextrin, crown compound, cyclophane, azacyclophane, calixarene, porphyrin, phthalocyanine, salen, and derivatives thereof. Preferably at least one or more types of molecules. These host molecules have a ring structure, and can recognize and contain a specific metal ion depending on the size, volume and shape of the inner pore of the ring structure.
  • the metal ion in the hygroscopic polymer material, it is possible to capture a salt of the metal ion having high hygroscopicity to the hygroscopic polymer material, and the moisture absorption of the hygroscopic polymer material Can be enhanced.
  • the crown compound is not particularly limited, and examples thereof include crown ether, benzocrown ether, dibenzocrown ether, aza crown ether and the like.
  • the crown ether is not particularly limited, and examples thereof include 12-crown-4, 15-crown-5, 18-crown-6 and the like.
  • 15-crown-5 having a reactive functional group that reacts with the hygroscopic polymeric material it can.
  • 15-crown-5 having a reactive functional group that reacts with a hygroscopic polymeric material include 2-hydroxymethyl-15-crown-5, 2-aminomethyl-15-crown-5, 1-aza- 15-crown-5 etc. can be mentioned.
  • 18-crown-6 having a reactive functional group that reacts with the hygroscopic polymer material is used.
  • Examples of 18-crown-6 having a reactive functional group that reacts with the hygroscopic polymer material include, for example, 2-hydroxymethyl-18-crown-6, 2-aminomethyl-18-crown-6, (+)- (18-crown-6) -2,11,12-tetracarboxylic acid, 1-aza-18-crown-6 and the like can be mentioned.
  • the benzocrown ether is not particularly limited, and examples thereof include benzo-18-crown-6, benzo-21-crown-7, and benzo-24-crown-8.
  • dibenzo crown ether examples include dibenzo-18-crown-6.
  • Examples of the azacrown ether include aza-12-crown-4, aza-15-crown-5, aza-18-crown-6 and the like.
  • Examples of aza-15-crown-5 include 1-aza-15-crown-5 and the like which can be bonded to the hygroscopic polymer material.
  • Examples of aza-18-crown-6 include 1-aza-18-crown-6 which can be bonded to the hygroscopic polymer material.
  • the crown compound is preferably selected and used according to the size of the metal ion to be captured.
  • the crown ether when including Li ion and Ca ion, the crown ether is preferably 15-crown-5 or aza-15-crown-5. Also, in the case of inclusion of K ion and Na ion, the crown ether is preferably 18-crown-6 or aza-18-crown-6.
  • the chelating agent may be polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polyalkylene glycol such as a copolymer of ethylene glycol and propylene glycol, ethylene diamine, bipyridine
  • it is at least one or more molecules selected from the group consisting of ethylenediaminetetraacetic acid, phenanthroline and derivatives thereof.
  • the molecule having a functional group is preferably at least one or more types of molecules selected from the group consisting of carboxylic acid, phosphoric acid, sulfonic acid, and amines.
  • examples of such molecules include poly (meth) acrylic acid, polystyrene sulfonic acid, polyallylamine and the like.
  • the hygroscopic material according to one embodiment of the present invention preferably further includes a salt of a monovalent, divalent or trivalent metal ion.
  • the salt include, but not limited to, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, aluminum chloride and the like.
  • the salt is more preferably a deliquescent salt. These salts may be used alone or in combination of two or more.
  • the hygroscopic material further contains a salt of the metal ion, the moisture absorption amount and the hygroscopic rate of the hygroscopic material can be improved.
  • the hygroscopic polymer material may contain a hydrophilic polymer.
  • a hydrophilic polymer for example, a hydrophilic polymer, a mixture containing a hydrophilic polymer, a copolymer containing a hydrophilic polymer, and an interpenetrating polymer network structure containing a hydrophilic polymer And semi-interpenetrating polymer networks containing hydrophilic polymers.
  • the hygroscopic polymer material can absorb moisture in the air by containing a hydrophilic polymer.
  • the hygroscopic material which concerns on one Embodiment of this invention contains the said hygroscopic polymeric material. That is, the hygroscopic material according to an embodiment of the present invention may be made of the hygroscopic polymer material, or may contain other components as long as the effects of the present invention are not adversely affected. Good.
  • the hygroscopic polymer material is more preferably any of the following (a) to (e).
  • (A) Hydrophilic polymer (b) A mixture of a stimulus-responsive polymer and a hydrophilic polymer whose affinity with water reversibly changes in response to external stimuli (c) Water in response to external stimuli A copolymer of a stimulus-responsive polymer and a hydrophilic polymer that reversibly changes in affinity with a polymer (d) A stimulus-responsive polymer in which affinity to water reversibly changes in response to an external stimulus Interpenetrating Polymer Network Structure of Water and Hydrophilic Polymer (e) Semi-interpenetrating Highness of Stimuli-Responsive Polymer and Hydrophilic Polymer whose Affinity with Water Reversibly Changes in Response to External Stimulus Molecular network structure (hydrophilic polymer)
  • hydrophilic polymer the polymer which has hydrophilic groups, such as a
  • hydrophilic polymer examples include polysaccharides such as alginic acid and hyaluronic acid; chitosan; cellulose derivatives such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxyethyl cellulose; poly (meth) acrylic acid and polymaleic acid , Polyvinyl sulfonic acid, polyvinyl benzene sulfonic acid, polyacrylamidoalkyl sulfonic acid, polydimethylaminopropyl (meth) acrylamide, these and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl ester etc.
  • polysaccharides such as alginic acid and hyaluronic acid
  • chitosan such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxyethyl cellulose
  • poly (meth) acrylic acid and polymaleic acid Polyvinyl
  • Polymer complex of poly (dimethylamino) propyl (meth) acrylamide and polyvinyl alcohol, complex of polyvinyl alcohol and poly (meth) acrylic acid, poly (meth) acrylic acid Nitrile, polyallylamine, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, poly (meth) acrylamide, poly-N, N'-dimethyl (meth) acrylamide, poly-2-hydroxyethyl methacrylate, poly-alkyl (meth) acrylate, poly Dimethylaminopropyl (meth) acrylamide, poly (meth) acrylonitrile and copolymers of the above-mentioned polymers can be mentioned.
  • the hydrophilic polymer is more preferably a crosslinked product of these.
  • hydrophilic polymer When the hydrophilic polymer is a crosslinked product, examples of such a crosslinked product include (meth) acrylic acid, allylamine, vinyl acetate, (meth) acrylamide, N, N'-dimethyl (meth) acrylamide, 2-hydroxyethyl.
  • a monomer such as methacrylate, alkyl (meth) acrylate, maleic acid, vinyl sulfonic acid, vinyl benzene sulfonic acid, acrylamido alkyl sulfonic acid, dimethylaminopropyl (meth) acrylamide, (meth) acrylonitrile, etc. is polymerized in the presence of a crosslinking agent. And polymers obtained by
  • crosslinking agent conventionally known ones may be appropriately selected and used, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, N, N′-methylene bis (meth) acrylamide, tri Crosslinkable monomers having a polymerizable functional group such as diisocyanate, divinylbenzene, polyethylene glycol di (meth) acrylate; glutaraldehyde; polyhydric alcohol; polyhydric amine; polyvalent carboxylic acid; metal such as calcium ion, zinc ion An ion etc. can be used suitably.
  • These crosslinking agents may be used alone or in combination of two or more.
  • a stimulus responsive polymer refers to a polymer that reversibly changes its properties in response to external stimuli.
  • the external stimulus is not particularly limited, and examples thereof include heat, light, an electric field, pH and the like.
  • the reversible change in affinity with water in response to an external stimulus means that the polymer exposed to the external stimulus is reversible between hydrophilicity and hydrophobicity in response to the external stimulus.
  • a stimulus-responsive polymer whose affinity with water reversibly changes in response to heat, that is, a temperature-responsive polymer is in the air by changing the temperature using a simple heating device. It can reversibly absorb water and release absorbed water. From this, the temperature responsive polymer can be particularly suitably used for a humidity controller.
  • Such a temperature responsive polymer is not particularly limited as long as it is a polymer having a lower critical solution temperature (LCST (Lower Critical Solution Temperature), hereinafter may be referred to as "LCST" in the present specification). Absent. Polymers with LCST are hydrophilic at low temperatures, but become hydrophobic above LCST. Here, LCST refers to the temperature at which the polymer dissolves in water when it is dissolved in water, but is hydrophilic and dissolves in water, but becomes hydrophobic when it becomes higher than a certain temperature and becomes insoluble. Say
  • examples of the temperature responsive polymer include, for example, poly (N-isopropyl (meth) acrylamide), poly (N-normalpropyl (meth) acrylamide), poly (N-methyl (meth) acrylamide) Poly (N-ethyl (meth) acrylamide), poly (N- normal butyl (meth) acrylamide), poly (N- isobutyl (meth) acrylamide), poly (N t- butyl (meth) acrylamide), etc.
  • N-alkyl (meth) acrylamide poly (N-vinyl isopropylamide), poly (N-vinyl normal propyl amide), poly (N-vinyl normal butyramide), poly (N-vinyl isobutyramide), poly ( Poly (N-vinylalkylamide) s such as N-vinyl-t-butylamide); Poly (N Vinylpyrrolidone); poly (2-alkyl-2-oxazoline) such as poly (2-ethyl-2-oxazoline), poly (2-isopropyl-2-oxazoline), poly (2-normalpropyl-2-oxazoline), etc.
  • Polyvinyl alkyl ethers such as polyvinyl methyl ether and polyvinyl ethyl ether; copolymers of polyethylene oxide and polypropylene oxide; poly (oxyethylene vinyl ether); cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose; Copolymers of polymers can be mentioned.
  • a cellulose derivative as the temperature-responsive polymer, it is not necessary to carry out polymerization, and therefore, the manufacture of the moisture absorbent is easy.
  • cellulose derivatives are safe and biodegradable and thus have the advantage of low environmental impact.
  • the preferred average molecular weight of hydroxypropyl cellulose is 2,000 to 2,000,000, and similarly, the preferred degree of substitution is 1 to 3.
  • the temperature responsive polymer is more preferably a crosslinked product of these polymers.
  • both the stimulus-responsive polymer and the hydrophilic polymer are crosslinked.
  • one of the stimulus-responsive polymer and the hydrophilic polymer is crosslinked. It is a body.
  • examples of such a crosslinked product include N-isopropyl (meth) acrylamide, N-normalpropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) ) N-alkyl (meth) acrylamides such as acrylamide, N-normal butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, etc .; N-vinyl isopropylamide, N-vinyl normal propyl N-vinyl alkyl amides such as amide, N-vinyl normal butyl amide, N-vinyl isobutyramide, N-vinyl t-butyl amide; vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl ether; ethylene oxide and propylene oxide A monomer such as 2-alkyl
  • crosslinking agent conventionally known ones may be appropriately selected and used, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, N, N′-methylene bis (meth) acrylamide, tri Crosslinkable monomers having a polymerizable functional group such as diisocyanate, divinylbenzene, polyethylene glycol di (meth) acrylate; glutaraldehyde; polyhydric alcohol; polyhydric amine; polyvalent carboxylic acid; metal such as calcium ion, zinc ion An ion etc. can be used suitably.
  • These crosslinking agents may be used alone or in combination of two or more.
  • the temperature responsive polymer is a crosslinked product
  • such a crosslinked product is obtained by reacting a non-crosslinked temperature responsive polymer, for example, the temperature responsive polymer exemplified above, with the crosslinking agent to form a network structure. It may be a crosslinked body obtained by forming
  • a stimulus-responsive polymer whose affinity to water reversibly changes in response to light
  • a light-responsive polymer such as an azobenzene derivative or a spiropyran derivative whose hydrophilicity or polarity is changed by light, temperature with them and temperature
  • a copolymer with at least one of a responsive polymer and a pH responsive polymer, a crosslinked product of the photoresponsive polymer, or a crosslinked product of the copolymer can be mentioned.
  • a polymer having a dissociative group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, a carboxyl group
  • a complex is formed by electrostatic interaction such as a complex of a containing polymer and an amino group-containing polymer, a hydrogen bond, or the like, or a crosslinked product thereof.
  • a stimulus responsive polymer whose affinity to water reversibly changes in response to pH
  • a polymer having a dissociative group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, etc., a carboxyl group
  • examples thereof include polymers in which a complex is formed by electrostatic interaction such as a complex of a containing polymer and an amino group-containing polymer, a hydrogen bond, or the like, or a crosslinked product thereof.
  • the molecular weight of the stimulus-responsive polymer is not particularly limited either, but it is preferable that the number average molecular weight determined by gel permeation chromatography (GPC) is 3000 or more.
  • hydrophilic polymer As the hygroscopic polymer material, the above-mentioned hydrophilic polymers can be used singly or in combination of two or more of the above-mentioned hydrophilic polymers. In such a case, a ligand having an affinity for a monovalent, divalent or trivalent metal ion is bound to a hydrophilic polymer.
  • the hydrophilic polymer itself is hydrophilic, and in addition to being capable of absorbing moisture in the air, the ligand binds to capture a salt of the metal ion having high hygroscopicity.
  • the hygroscopic property of the hygroscopic polymeric material can be enhanced.
  • the metal ion salt is simply mixed using the hydrophilic polymer containing no ligand, the metal ion salt is uniformly dispersed by uniformly dispersing the ligand. Because it can, it can enhance the hygroscopicity.
  • bonded with the said hydrophilic polymer is an effect obtained also in any hygroscopic polymeric material containing a hydrophilic polymer. Therefore, similar effects can be obtained in the cases of (b) to (e) described below.
  • a stimulus-responsive polymer or a mixture of two or more types of stimulus-responsive polymers whose affinity to water reversibly changes in response to the aforementioned external stimulus can be used.
  • a ligand having an affinity for a monovalent, divalent or trivalent metal ion is bound to at least one of the stimulus-responsive polymer and the hydrophilic polymer.
  • the hygroscopic polymer material is, for example, a simple heating device because of the nature of the stimulus-responsive polymer's affinity to water reversibly changing in response to external stimuli. By changing the temperature, absorption of moisture in the air and release of the absorbed moisture can be reversibly performed. Further, by binding the ligand to the hygroscopic polymer material, salts of the metal ions having high hygroscopicity can be captured, and the hygroscopicity of the hygroscopic polymer material can be enhanced. it can.
  • the metal ion salt is simply mixed using the hygroscopic polymer material not containing the ligand, the metal ion salt is uniformly dispersed by uniformly dispersing the ligand.
  • the hygroscopicity can be enhanced.
  • the metal ion salt when the metal ion salt is simply mixed using the hygroscopic polymer material not containing the ligand, when the hygroscopic polymer material containing the stimulus-responsive polymer releases the absorbed water, There is a problem that the metal ion salt leaks out with the released water.
  • the leakage of the metal ion salt By the leakage of the metal ion salt, the hygroscopicity of the hygroscopic material is lowered while the absorption of the moisture in the air and the release of the absorbed moisture are repeated.
  • the ligand retains the metal ion by binding the ligand to the hygroscopic polymer material, it is possible to prevent the salt of the metal ion from leaking together with the released water. Can.
  • the donor potential barrier is maintained while the metal ions are ionized, so that the leakage of the metal ions can be effectively suppressed.
  • the said effect by the said hygroscopic polymeric material containing a stimulus-responsive polymer is an effect obtained also in any hygroscopic polymeric material containing a stimulus-responsive polymer. Therefore, similar effects can be obtained in the cases of (c) to (e) described below.
  • the proportions of the stimulus-responsive polymer and the hydrophilic polymer contained in the hygroscopic polymer material are not particularly limited, but the stimulus response is the proportion of the weight excluding the weight of the crosslinking agent.
  • the hydrophilic polymer is more preferably contained in an amount of 5% by weight or more, still more preferably 20% by weight or more, still more preferably 1000% by weight or less, based on the amount of the polymer. It is included by weight or less.
  • a stimulus-responsive polymer or a mixture of two or more types of stimulus-responsive polymers whose affinity to water reversibly changes in response to the aforementioned external stimulus can be used.
  • a ligand having an affinity for a monovalent, divalent or trivalent metal ion is bound to at least one of the stimulus-responsive polymer and the hydrophilic polymer.
  • the copolymer is not particularly limited as long as it is a polymer including a constituent unit constituting the stimulus-responsive polymer and a constituent unit constituting the hydrophilic polymer.
  • the ratio of the constituent unit constituting the stimulus-responsive polymer to the constituent unit constituting the hydrophilic polymer to the total constituent units contained in the hygroscopic polymer material is not particularly limited,
  • the structural unit constituting the hydrophilic polymer is more preferably 30 mol% or more, still more preferably 40 mol% or more, based on the structural unit constituting the stimulus-responsive polymer.
  • an interpenetrating polymer network of the above-described stimulus-responsive polymer or a mixture of two or more types of stimulus-responsive polymers and the above-described (a) can be used.
  • the interpenetrating polymer network structure all different types of polymers are cross-linked polymers, and the cross-linked networks of the respective polymers mutually independently exist without being chemically bonded. An intertwined structure.
  • the hydrophilic polymer and the stimulus-responsive polymer are both crosslinked polymers, and the crosslinked network of the hydrophilic polymer and the stimulus response It refers to a structure in which a cross-linked network of a sex polymer entangles with each other in a state of being independently present without being chemically bonded.
  • the hydrophilic polymer or the stimulus-responsive polymer is a mixture, at least one hydrophilic polymer and the stimulus-responsive polymer in the mixture form an interpenetrating polymer network structure. Just do it.
  • the affinity to water is more responsive to external stimuli than in the case of using a mixture or copolymer of the hydrophilic polymer and the stimulus-responsive polymer. It changes more clearly and reversibly. Therefore, by applying an external stimulus, absorption of moisture in the air and release of the absorbed moisture can be performed more efficiently, so it can be particularly suitably used in a humidity controller.
  • the proportions of the stimulus-responsive polymer and the hydrophilic polymer contained in the hygroscopic polymer material are not particularly limited, but the stimulus response is the proportion of the weight excluding the weight of the crosslinking agent.
  • the hydrophilic polymer is more preferably contained in an amount of 5% by weight or more, still more preferably 20% by weight or more, still more preferably 1000% by weight or less, based on the amount of the polymer. It is included by weight or less.
  • a semi-interpenetrating polymer network structure of the above-described stimulus-responsive polymer or a mixture of two or more types of stimulus-responsive polymers and the above-described (a) can be used.
  • one of the different types of polymers is a crosslinked polymer, and the other is a linear polymer or a non-crosslinked polymer, and each polymer is chemically It refers to a mutually intertwined structure in an independently existing state without being bonded. That is, the stimulus-responsive polymer or the mixture of two or more types of stimulus-responsive polymers, and the semi-interpenetrating polymer network structure with the hydrophilic polymer are the hydrophilic polymer and the stimulus-responsive property.
  • One of the polymers is a crosslinked polymer, the other is a non-crosslinked polymer, and the stimulus-responsive polymer and the hydrophilic polymer are independently present without being chemically bonded.
  • the hydrophilic polymer or the stimulus-responsive polymer is a mixture
  • at least one hydrophilic polymer and the stimulus-responsive polymer in the mixture form a semi-interpenetrating polymer network structure. Just do it.
  • the semi-interpenetrating polymer network it is more compatible with water in response to external stimuli than in the case of using a mixture or copolymer of the hydrophilic polymer and the stimulus-responsive polymer. Changes more clearly and reversibly. Therefore, by applying an external stimulus, absorption of moisture in the air and release of the absorbed moisture can be performed more efficiently, so it can be particularly suitably used in a humidity controller.
  • the proportions of the stimulus-responsive polymer and the hydrophilic polymer contained in the hygroscopic polymer material are not particularly limited, but the stimulus response is the proportion of the weight excluding the weight of the crosslinking agent.
  • the hydrophilic polymer is more preferably contained in an amount of 5% by weight or more, still more preferably 20% by weight or more, still more preferably 1000% by weight or less, based on the amount of the polymer. It is included by weight or less.
  • the ratio of the ligand contained in the hygroscopic polymer material to the total structural unit of the polymer contained in the hygroscopic polymer material is 10 It is preferably from mol% to 80 mol%, more preferably from 30 mol% to 80 mol%, still more preferably from 40 mol% to 70 mol%. If the ratio of the ligand is 40 mol% or more, the ratio of the metal ion contained in the hygroscopic material is also high, which is preferable because the hygroscopicity is improved.
  • the ratio of the ligand is 70 mol% or less, it is preferable because the release of absorbed water is not affected when using the stimulus-responsive polymer.
  • being included in the hygroscopic polymer material means existing in the hygroscopic polymer material, regardless of whether it is bound to the hygroscopic polymer material or not.
  • the ligand is bound to the hygroscopic polymeric material.
  • the ratio of the ligand bonded to the hygroscopic polymer material to the total structural units of the polymer contained in the hygroscopic polymer material is more preferably 10 mol% to 80 mol%, and 40 mol % To 70 mol% is more preferable. If the ratio of the ligand is 40 mol% or more, the ratio of the metal ion contained in the hygroscopic material is also high, which is preferable because the hygroscopicity is improved. If the ratio of the ligand is 70 mol% or less, it is preferable because the release of absorbed water is not affected when using the stimulus-responsive polymer.
  • the shape of the hygroscopic material according to one embodiment of the present invention is not particularly limited, and may be plate-like, sheet-like, film-like or particulate.
  • the shape of the particulate hygroscopic material is also not particularly limited, but may be, for example, a substantially spherical shape, a plate-like shape, or the like.
  • the size of the hygroscopic material according to the present invention is also not particularly limited, and may be appropriately selected in accordance with the configuration of the humidity controller when it is used in the humidity controller.
  • the hygroscopic polymer material is preferably a dried product dried by, for example, reduced pressure (vacuum) drying, heat drying, natural drying, a combination thereof, or the like, and is a dried product dried by reduced pressure drying or heat drying. It is more preferable that By drying under reduced pressure or heat, the hygroscopic polymer material forms fine pores when the solvent used for polymerization is sublimated and goes outside, and forms a dry matter of the hygroscopic polymer material having a dense network structure. can do. Since the hygroscopic polymer material having a dense network structure has a large area in contact with air, the proportion of the amount of absorbing moisture in the air is high.
  • the hygroscopic polymeric material which has a dense network structure can suppress the leak of the salt of a metal ion by the close entanglement of molecular chains.
  • the hygroscopic polymer material having a dense network structure is a hygroscopic polymer which is not bound to a ligand even when absorbing moisture in the air or when discharging water due to a stimulus such as heating. The presence of the functional groups of the material preserves the electrical neutralization within the hygroscopic polymeric material so that the equilibrium state can be maintained after the metal ion salt is released with the water release.
  • the degree of reduced pressure when drying by reduced pressure drying is preferably 10 Pa to 100 Pa, and more preferably 20 Pa to 50 Pa.
  • the vacuum drying is more preferably freeze drying, which is performed after freezing the hygroscopic polymer material.
  • freeze drying By freezing and drying the hygroscopic polymer material under reduced pressure, the hygroscopic polymer material generates fine pores when the solvent used for polymerization is sublimated and goes outside, and the hygroscopic polymer material has a denser network structure. Can form a dry body of the polymeric material.
  • the freezing temperature is preferably ⁇ 60 ° C. to ⁇ 20 ° C., and more preferably ⁇ 60 ° C. to ⁇ 30 ° C.
  • the drying time is preferably 20 hours or more, and more preferably 30 hours or more.
  • the upper limit of the drying time is preferably about 50 hours.
  • the dried hygroscopic polymer material does not have to completely remove the water from the hygroscopic polymer material, and if it can absorb the water in the air, May be included. Therefore, the moisture content of the dry body of the hygroscopic polymer material is not particularly limited as long as the dry body can absorb the moisture in the air, but it is, for example, 10% by weight to 30% by weight. It is preferable that there be 20% by weight to 25% by weight.
  • the water content refers to the ratio of water to the dry weight of the hygroscopic polymer material.
  • the description regarding the said dried body is related to a hygroscopic polymeric material, the same may be said of a hygroscopic material.
  • a method of manufacturing a hygroscopic material according to an embodiment of the present invention is a hygroscopic material containing a hygroscopic polymer material, wherein the hygroscopic polymer material contains a hydrophilic polymer, and the hygroscopic polymer is This is a method for producing a hygroscopic material in which a ligand having an affinity to a monovalent, divalent or trivalent metal ion is bound to a material.
  • a method of manufacturing a hygroscopic material in one embodiment of the present invention is a hygroscopic polymer material containing a hydrophilic polymer, wherein the hygroscopic polymer material is a monovalent, divalent or trivalent metal ion.
  • the method may further include a grinding step of grinding the hygroscopic polymeric material dried in the drying step.
  • the hygroscopic polymeric material production process is not particularly limited as long as it is a process capable of producing the hygroscopic polymeric material, but the hygroscopic polymeric material is produced, for example, by the following method be able to.
  • a monomer forming the hydrophilic polymer, a monomer forming the stimulus-responsive polymer, and the ligand are reacted with each other to form at least a part of the ligand as a monomer forming the hydrophilic polymer and / or Or the step (i) of respectively bonding to the monomer constituting the stimulus responsive polymer, the monomer constituting the hydrophilic polymer and the monomer constituting the stimulus responsive polymer, which are obtained in the step (i) And copolymerization step (ii).
  • a semi-interpenetrating polymer network structure comprising a crosslinked network (a) and the non-crosslinked hydrophilic polymer by polymerizing a monomer constituting the hydrophilic polymer in the presence of the crosslinked network (a)
  • hydrophilic polymer to which the ligand is bound and the stimulus-responsive polymer to which the ligand is bound are mixed.
  • a polymer to which the ligand is not bound may be used as either one of the polymer and the stimulus-responsive polymer.
  • an interpenetrating polymer network is formed between the hydrophilic polymer to which the ligand is bound and the stimulus-responsive polymer to which the ligand is bound.
  • the hydrophilic polymer and the stimulus responsive polymer those to which the ligand is not bound may be used.
  • the polymerization method for polymerizing the monomers is not particularly limited, and radical polymerization, ionic polymerization, polycondensation, ring-opening polymerization, etc. may be suitably used. it can.
  • the solvent used for the polymerization may be appropriately selected according to the monomer, but, for example, water, phosphate buffer, Tris buffer, acetate buffer, methanol, ethanol and the like can be suitably used.
  • the polymerization initiator is also not particularly limited.
  • persulfates such as ammonium persulfate and sodium persulfate; hydrogen peroxide; peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, azobis Isobutyronitrile, benzoyl peroxide and the like can be suitably used.
  • an initiator showing oxidation such as persulfates and peroxides, may be, for example, sodium bisulfite, N, N, N ', N'- tetramethylethylenediamine, etc. It can also be used as a redox initiator. Alternatively, light, radiation or the like may be used as an initiator.
  • the polymerization temperature is not particularly limited, but is usually 5 ° C to 80 ° C.
  • the polymerization time is also not particularly limited, but is usually 4 hours to 48 hours.
  • the concentration of the monomer, the crosslinking agent and the like in the polymerization is not particularly limited as long as it is a concentration at which the stimulus-responsive polymer, the hydrophilic polymer, or a crosslinked product thereof can be obtained. Further, the concentration of the polymerization initiator is also not particularly limited and may be appropriately selected.
  • a method of forming a crosslinked network of the cross-linked body of the stimulus-responsive polymer or the hydrophilic polymer by polymerizing and crosslinking the monomer includes a crosslinking agent for the monomer
  • the method may be a method of polymerizing in the presence of or a method of polymerizing monomers to form a polymer and then crosslinking with a crosslinking agent.
  • step (iv) of the above [7] [9] and [11] under appropriate polymerization conditions or crosslinking conditions such that no crosslinking is formed with the polymer formed in the step (ii) or the crosslinked product thereof It should be selected.
  • step (iii) of the above [8] [10] and [12] polymerization conditions or crosslinking conditions such that no crosslinking is formed with the polymer formed in the step (i) or the crosslinked product thereof. Is selected as appropriate.
  • the monomer constituting the stimulus-responsive polymer, the monomer constituting the hydrophilic polymer, and the crosslinking agent are as described in the above (I).
  • the stimulus-responsive polymer or the hydrophilic polymer is a polymer such as a cellulose derivative or a polysaccharide from the beginning
  • the stimulus response Polymerizing and cross-linking the monomer that constitutes the functional polymer is “to crosslink the stimulus-responsive polymer”
  • “to polymerize and crosslink the monomer that constitutes the hydrophilic polymer” is “that the hydrophilic property is It is read as “crosslinking polymer”.
  • the hydrophilicity is obtained in the presence of the stimulus-responsive polymer obtained or the crosslinked product thereof.
  • Polymer or crosslinked polymer thereof but after producing the hydrophilic polymer or crosslinked polymer thereof, the stimulus-responsive property is high in the presence of the obtained hydrophilic polymer or crosslinked polymer thereof It is also possible to produce molecules or crosslinks thereof.
  • the interpenetrating polymer network structure or the semi-interpenetrating polymer network structure is obtained after the stimulus-responsive polymer or the crosslinked product thereof is produced.
  • the hydrophilic polymer or the crosslinked product thereof is produced in a two-step process of producing the hydrophilic polymer or the crosslinked product thereof in the presence of the stimulus responsive polymer or the crosslinked product thereof, If polymerization conditions or crosslinking conditions are selected such that no crosslinking is formed between the hydrophilic polymer or the crosslinked body thereof and the stimulus-responsive polymer or the crosslinked body thereof and the hydrophilic polymer or the crosslinked body thereof It can also be done simultaneously in one step.
  • the hygroscopic polymeric material can be manufactured by a one-step process.
  • the drying step the hygroscopic polymeric material obtained in the hygroscopic polymeric material manufacturing step is dried to obtain a dried hygroscopic polymeric material.
  • the method for drying the hygroscopic polymer material is not particularly limited, and conventionally known methods can be appropriately used. Examples of the method of drying the hygroscopic polymeric material include drying by heating, drying under reduced pressure, lyophilization, solvent substitution method and the like.
  • the method of pulverization is not particularly limited, but, for example, the dry body of the hygroscopic polymeric material is pulverized using a mechanical pulverizer such as a rotor, a ball mill, a pneumatic pulverizer, etc. According to the above, further classification can be performed to obtain a particulate hygroscopic material.
  • a mechanical pulverizer such as a rotor, a ball mill, a pneumatic pulverizer, etc.
  • further classification can be performed to obtain a particulate hygroscopic material.
  • the particulate hygroscopic material can also be manufactured by synthesizing hygroscopic polymer material fine particles by using emulsion polymerization in the hygroscopic polymer material manufacturing process.
  • the hygroscopic material according to the present invention in particular, the hygroscopic material containing the hydrophilic polymer and the stimulus-responsive polymer can reversibly absorb water in the air and release the absorbed water, it can be used as a humidity controller. It can be particularly suitably used, and according to the humidity control apparatus using the hygroscopic material, humidity control can be efficiently performed without using overcooling or a large amount of heat. Therefore, a humidity controller using the moisture absorbent according to one embodiment of the present invention is also included in the present invention. Hereinafter, a humidity controller according to an embodiment of the present invention will be described.
  • a humidity control apparatus is a hygroscopic material containing a hygroscopic polymeric material, wherein the hygroscopic polymeric material contains a hydrophilic polymer and a stimulus responsive polymer, In order to reduce the affinity of the stimulus-responsive polymer to water, the hygroscopic material in which a ligand having an affinity to a monovalent, divalent, or trivalent metal ion is bound to a hygroscopic polymer material is used. And a stimulus applying unit for applying an external stimulus.
  • the hygroscopic material preferably further contains a salt of a monovalent, divalent or trivalent metal ion.
  • the description is abbreviate
  • a humidity control apparatus is provided with a humidity control main body having an intake port and an exhaust port. Inside the humidity control body, a plurality of humidity control units carrying the moisture absorbing material of the present invention, a humidity control area where the humidity control unit absorbs moisture in the air, and moisture in the air are absorbed Dehydration area, which discharges the moisture absorbed by the humidity control unit as water, a drainage tank storing the released water, and the air to be absorbed are taken in from the air intake port, and the absorbed air is discharged from the exhaust port And a blower fan for the purpose.
  • the humidity control material is a humidity control material containing a hygroscopic polymer material
  • the hygroscopic polymer material contains a hydrophilic polymer and water in response to an external stimulus.
  • a stimulus-responsive polymer that reversibly changes its affinity, wherein a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bound to the hygroscopic polymer material.
  • the plurality of humidity control units are movable between the humidity control area and the dehydration area.
  • the dehydration area is provided with a stimulus applying unit for applying an external stimulus for reducing the affinity of the stimulus-responsive polymer with water.
  • the stimulus applying unit is, for example, a heater.
  • Air sucked into the humidity control device comes in contact with the hygroscopic material of the humidity control unit when passing through the humidity control area.
  • a hygroscopic material that is hydrophilic at room temperature absorbs moisture in the air (moist air), whereby the moist air is absorbed when passing through the humidity control area, and the absorbed air (dry air) is exhausted. Exhausted from
  • the humidity control unit that has absorbed the moisture in the air moves from the humidity control area into the dehydration area.
  • the moisture application material becomes hydrophobic by the external stimulus being applied to the moisture absorption material by the stimulus application unit.
  • the moisture absorbed by the hygroscopic material is released from the hygroscopic material as water. Then, the released water is discharged to a drainage tank.
  • the ligand is held by the metal ion because the ligand is bound to the hygroscopic polymer material of the hygroscopic material, and thus the metal ion is released.
  • the water it is possible to prevent the salt of the metal ion from leaking out. Therefore, even if absorption of moisture in the air and release of absorbed moisture by the hygroscopic material are repeated by repeatedly moving the humidity control unit between the humidity control area and the dehydration area, It is possible to suppress the hygroscopicity of the hygroscopic material.
  • the hygroscopic material according to aspect 1 of the present invention is a hygroscopic material containing a hygroscopic polymeric material, and the hygroscopic polymeric material contains a hydrophilic polymer, and the hygroscopic polymeric material contains 1 It has a configuration in which a ligand having an affinity to a divalent, divalent or trivalent metal ion is bound.
  • the ligand is a host molecule forming a clathrate compound, a chelating agent, or a molecule having a functional group capable of ionically bonding with the metal ion.
  • a salt of the metal ion having high hygroscopicity can be captured in the hygroscopic polymeric material, and hygroscopicity of the hygroscopic polymeric material can be enhanced.
  • the host molecule is a group consisting of cyclodextrin, a crown compound, cyclophane, azacyclophane, calixarene, porphyrin, phthalocyanine, salen, and derivatives thereof. It has a configuration that is at least one or more types of molecules selected from among the above.
  • a salt of the metal ion having high hygroscopicity can be captured in the hygroscopic polymeric material, and hygroscopicity of the hygroscopic polymeric material can be enhanced.
  • the chelating agent is at least one selected from the group consisting of polyalkylene glycol, ethylene diamine, bipyridine, ethylene diamine tetraacetic acid, phenanthroline, and derivatives thereof.
  • the composition is a molecule of
  • a salt of the metal ion having high hygroscopicity can be captured in the hygroscopic polymeric material, and hygroscopicity of the hygroscopic polymeric material can be enhanced.
  • the molecule having a functional group is at least one or more types of molecules selected from the group consisting of carboxylic acid, phosphoric acid, sulfonic acid, and amines. It has a certain configuration.
  • a salt of the metal ion having high hygroscopicity can be captured in the hygroscopic polymeric material, and hygroscopicity of the hygroscopic polymeric material can be enhanced.
  • the hygroscopic polymeric material has a configuration as any of the following (a) to (e).
  • (A) Hydrophilic polymer (b) A mixture of a stimulus-responsive polymer and a hydrophilic polymer whose affinity with water reversibly changes in response to external stimuli (c) Water in response to external stimuli A copolymer of a stimulus-responsive polymer and a hydrophilic polymer that reversibly changes in affinity with a polymer (d) A stimulus-responsive polymer in which affinity to water reversibly changes in response to an external stimulus Interpenetrating Polymer Network Structure of Water and Hydrophilic Polymer (e) Semi-interpenetrating Highness of Stimuli-Responsive Polymer and Hydrophilic Polymer whose Affinity with Water Reversibly Changes in Response to External Stimulus Molecular network structure According to the above-mentioned configuration (a), the hydrophilic polymer
  • the metal ion salt is simply mixed using the hydrophilic polymer containing no ligand, the metal ion salt is uniformly dispersed by uniformly dispersing the ligand. Because it can, it can enhance the hygroscopicity.
  • the hygroscopic material according to aspect 7 of the present invention is any one of the above-mentioned aspects 1 to 6, wherein the ligand for the total structural unit of the polymer contained in the hygroscopic polymeric material is the ligand bound to the hygroscopic polymeric material The proportion is in the range of 10% by mole to 80% by mole.
  • the hygroscopicity of the hygroscopic material is preferably improved, and the use of the stimulus-responsive polymer is preferable because it does not affect the release of absorbed water.
  • the hygroscopic material according to aspect 8 of the present invention has a configuration further including a salt of a monovalent, divalent or trivalent metal ion in any of the above aspects 1 to 7.
  • Example 1 Synthesis of Alg-PEG (CaCl 2 / LiCl) / HPC Semi-Interpenetrating Polymer Network> 100 mg of sodium alginate (Alg) and 10 wt% of polyethylene glycol diglycidyl ether (PEGDE) with respect to Alg were dissolved in 100 ml of ultrapure water. The resulting aqueous solution was heated at 70 ° C. for 11 hours.
  • Alg-PEG CaCl 2 / LiCl
  • HPC Semi-Interpenetrating Polymer Network 100 mg of sodium alginate (Alg) and 10 wt% of polyethylene glycol diglycidyl ether (PEGDE) with respect to Alg were dissolved in 100 ml of ultrapure water. The resulting aqueous solution was heated at 70 ° C. for 11 hours.
  • PEGDE polyethylene glycol diglycidyl ether
  • the heated aqueous solution was mixed with an aqueous solution of hydroxypropyl cellulose (HPC) (an aqueous solution of HPC (Wako Pure Chemical Industries, Ltd., hydroxypropyl cellulose 150 to 400 cP) dissolved in 100 ml of ultrapure water).
  • HPC hydroxypropyl cellulose
  • a polymer gel (Alg-PEG (CaCl 2 / LiCl) / HPC semi-interpenetrating polymer network) in which CaCl 2 / LiCl is trapped in the molecular network is obtained.
  • the obtained polymer gel was frozen at -30 ° C and dried under a reduced pressure condition of 20 Pa for 36 hours so that CaCl 2 / LiCl was trapped in the Alg-PEG / HPC semi-interpenetrating polymer network,
  • a dried polymer gel (hygroscopic material 1) was obtained.
  • the ratio of the ligand to the total constituent units of the polymer contained in the hygroscopic material 1 was about 5 mol%.
  • Example 2 In the same manner as in Example 1 except that the amount of PEGDE added to alginic acid (Alg) sodium was 20 wt% relative to Alg, an Alg-PEG / HPC semi-interpenetrating polymer network was prepared with CaCl 2 / LiCl The obtained polymer gel was dried (hygroscopic material 2). The ratio of the ligand to the total constituent units of the polymer contained in the hygroscopic material 2 was about 10 mol%.
  • Example 3 In the same manner as in Example 1 except that the amount of PEGDE added to alginic acid (Alg) sodium was 30 wt% relative to Alg, an Alg-PEG / HPC semi-interpenetrating polymer network was prepared with CaCl 2 / LiCl The resulting polymer gel was dried (hygroscopic material 3). The ratio of the ligand to the total constituent units of the polymer contained in the hygroscopic material 3 was about 15 mol%.
  • Comparative Example 1 Synthesis of Alg / HPC Semi-Interpenetrating Polymer Network Structure> A mixture of a dried Alg / HPC semi-interpenetrating polymer network and CaCl 2 / LiCl (comparative moisture absorption) in the same manner as in Example 1 except that the amount of PEGDE added to alginic acid (Alg) sodium is 0. Obtained wood 1).
  • the time-moisture absorption rate is shown in FIG.
  • the vertical axis indicates the moisture content (in FIG. 1, "Amount of moisture absorption".
  • the moisture content is, in other words, the amount of moisture absorbed in the air. Unit: g / g-dry matter ( In FIG. 1, "g / g-dried polymer” is described)), and the horizontal axis shows time (unit: hour).
  • the higher the proportion of PEG attached to Alg the better the moisture absorption.
  • the amount of PEG is large, the amount of coordinated Ca ion and Li ion is also increased.
  • Example 4 Synthesis of Alg-CE (CaCl 2 / LiCl)> 1 g of sodium alginate (Alg) was dissolved in 100 ml of ultrapure water. In order to react 50 mol% of carboxyl groups in Alg with the obtained Alg aqueous solution, 735 mg of ethylene dichloride (EDC) and 437 mg of N-hydroxysuccinimide (NHS) are added and stirred for 30 minutes, EDC / NHS activated Alg An aqueous solution was prepared.
  • EDC ethylene dichloride
  • NHS N-hydroxysuccinimide
  • a CE aqueous solution in which 690 mg of 2-aminomethyl-15-crown-5 (CE) is dissolved in 10 ml of ultrapure water is added dropwise to an EDC / NHS activated Alg aqueous solution and stirred for 8 hours, an aqueous solution containing Alg-CE I got
  • the aqueous solution containing Alg-CE was dialyzed into ultrapure water using a cellulose dialysis membrane, and was purified by passive diffusion to remove small molecules having a molecular weight less than the molecular weight cut off in the solution. Thereafter, the purified Alg-CE was dissolved in ultrapure water to prepare an Alg-CE aqueous solution.
  • Comparative Example 2 1 g of sodium alginate (Alg) was dissolved in 100 ml of ultrapure water. To the obtained Alg aqueous solution, 200 ml of a 0.5 M each CaCl 2 / LiCl aqueous solution was added and allowed to stand for 30 hours to obtain a polymer gel which is a mixture of Alg and CaCl 2 / LiCl. The obtained polymer gel is frozen at -30 ° C and dried under a reduced pressure of 20 Pa for 36 hours to obtain a dried polymer gel (comparative moisture absorbent 2) which is a mixture of Alg and CaCl 2 / LiCl. Obtained.
  • Time-hygroscopicity is shown in FIG.
  • the vertical axis indicates the moisture content (“Amount of moisture absorption” in FIG. 2.
  • the moisture content is, in other words, the amount of moisture absorbed in the air.
  • the horizontal axis shows time (unit: hour).
  • the hygroscopic material 4 in which CE is bonded to Alg has a higher moisture absorption rate than the comparative hygroscopic material 2 in which CE is not bonded to Alg.
  • CE is for inclusion of Ca ions and Li ions.
  • the hygroscopic material according to the present invention is very useful as a hygroscopic and dehydrating material, and can be suitably used for a humidity controller.

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Abstract

L'invention fournit un matériau d'absorption d'humidité qui tout en prévenant la fuite d'un liquide déliquescent, dans le cas où il contient un sel inorganique déliquescent, se révèle excellent du fait de ses propriétés absorbantes. Plus précisément, l'invention concerne un matériau d'absorption d'humidité qui contient un matériau polymère d'absorption d'humidité comprenant un polymère hydrophile, lequel matériau polymère d'absorption d'humidité présente une liaison d'un ligand ayant une affinité avec des ions métalliques monovalents, bivalents ou trivalents
PCT/JP2018/001652 2017-09-01 2018-01-19 Matériau d'absorption d'humidité WO2019043977A1 (fr)

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WO2022271101A3 (fr) * 2021-06-21 2023-03-02 National University Of Singapore Film composite hygroscopique autostable
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