CN111050883A - Moisture-absorbing material - Google Patents

Moisture-absorbing material Download PDF

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CN111050883A
CN111050883A CN201880052362.1A CN201880052362A CN111050883A CN 111050883 A CN111050883 A CN 111050883A CN 201880052362 A CN201880052362 A CN 201880052362A CN 111050883 A CN111050883 A CN 111050883A
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polymer
moisture
stimulus
hygroscopic
ligand
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崎川伸基
宫田隆志
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Sharp Corp
Kansai University
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Kansai University
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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

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  • Drying Of Gases (AREA)
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Abstract

In the case where the deliquescent inorganic salt is contained, leakage of the deliquescent liquid is prevented and a moisture-absorbent material more excellent in hygroscopicity is realized. A moisture-absorbing material comprising a moisture-absorbing polymer material which contains a hydrophilic polymer and is bonded to a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is used.

Description

Moisture-absorbing material
Technical Field
The present invention relates to a moisture-absorbing material.
Background
Conventionally, deliquescent inorganic salts such as calcium chloride, magnesium chloride, and aluminum chloride have been used as hygroscopic materials. The deliquescent inorganic salt is excellent in hygroscopicity, but has a problem that it is easily liquefied after moisture absorption and the liquid leaks to contaminate the damaged surroundings. As moisture-absorbing materials for solving this problem, there are known a dry material containing a deliquescent inorganic salt and a nonionic cellulose derivative as a gelling agent (see patent document 1), a dehumidifying composition composed of a deliquescent inorganic salt, a hydrophilic polymer, and cellulose powder (see patent document 2), and the like.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2010-194497 "
Patent document 2: japanese laid-open patent publication No. 2000-5553 "
Disclosure of Invention
Technical problem to be solved by the invention
However, the conventional techniques described above can prevent leakage of the deliquescent liquid to some extent when the deliquescent inorganic salt is contained, but are not sufficient in terms of hygroscopicity.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a moisture-absorbing material which can prevent leakage of a moisture-decomposing liquid and has more excellent moisture absorption properties when the moisture-decomposing inorganic salt is contained.
Means for solving the problems
A moisture-absorbing material according to an embodiment of the present invention is a moisture-absorbing material containing a moisture-absorbing polymer material for solving the above-described problem, wherein the moisture-absorbing polymer material contains a hydrophilic polymer, and a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded to the moisture-absorbing polymer material.
Effects of the invention
As described above, the moisture-absorbing material according to an embodiment of the present invention is a moisture-absorbing material containing a moisture-absorbing polymer material, and includes: the hygroscopic polymer material contains a hydrophilic polymer, and a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded to the hygroscopic polymer material, and therefore the following effects are obtained: a salt capable of capturing the metal ion having a high hygroscopicity, and a moisture-absorbing material capable of preventing leakage of deliquescent liquid derived from the salt and having a more excellent hygroscopicity.
Drawings
Fig. 1 is a graph showing the results of evaluating the moisture absorption characteristics of a moisture absorbing material in examples of the present invention.
Fig. 2 is a graph showing the results of evaluating the moisture absorption characteristics of the moisture absorbing material in the example of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to this, and various modifications can be made within the scope described above, and embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the technical scope of the present invention. In addition, "a to B" indicating a numerical range means "a to B" unless otherwise specified in the present specification. Further, "mass" and "weight" may be considered synonyms. In addition, when any of "acryl" or "methacryl" is represented, it is denoted by "(meth) acryl".
[ first embodiment: moisture-absorbing material
The present inventors have conducted extensive studies in view of the above-mentioned problems, and as a result, have found that a moisture-absorbing material containing a hydrophilic polymer and having a ligand having an affinity for a monovalent, divalent, or trivalent metal ion bonded to the moisture-absorbing polymer material can capture a salt of the metal ion having a high moisture-absorbing property, and can realize a moisture-absorbing material having a further excellent moisture-absorbing property while preventing leakage of a deliquescent liquid derived from the salt, thereby completing the present invention.
That is, a moisture-absorbing material according to an embodiment of the present invention is a moisture-absorbing material containing a moisture-absorbing polymer material, and includes: the hygroscopic polymer material contains a hydrophilic polymer, and a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded to the hygroscopic polymer material.
A moisture-absorbing material according to an embodiment of the present invention includes a moisture-absorbing polymer material in which a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded. The ligand has an affinity for a monovalent, divalent, or trivalent metal ion, and is therefore capable of capturing the monovalent, divalent, or trivalent metal ion. Therefore, the salt of the metal ion having high hygroscopicity can be captured by the hygroscopic polymer material, and the hygroscopicity of the hygroscopic polymer material can be improved. A conventional absorbent material containing a deliquescent inorganic salt and a polymer as a gelling agent is obtained by mixing the deliquescent inorganic salt with the polymer as the gelling agent. The moisture-absorbent material according to an embodiment of the present invention has higher moisture absorption than the conventional moisture-absorbent material. The reason for this is considered to be that the ligand can be uniformly dispersed in the hygroscopic polymer material, and thus the salt of the metal ion can be more uniformly dispersed, and more efficient moisture absorption can be achieved.
In the present invention, "bonding" in the description of "ligand bonded" is not limited to this, but bonding is preferably performed via a chemical bond such as a covalent bond, an ionic bond, or a coordinate bond, and more preferably bonding is performed via a covalent bond. Thus, the ligand is stably immobilized in the hygroscopic polymer material. More specifically, a reactive functional group is introduced into a ligand, and the reactive functional group is reacted with a hygroscopic polymer material, whereby the ligand is suitably bonded to the hygroscopic polymer material. The bonding to the hygroscopic polymer material may be any bonding to any polymer contained in the hygroscopic polymer material.
(I) Ligands having affinity for monovalent, divalent, or trivalent metal ions
Examples of the monovalent metal ion include Li+、Na+、K+、Rb+、Cs+And the like. Examples of the divalent metal ion include Mg2+、Ca2+、Sr2+、Ba2+And the like. Examples of the trivalent metal ion include Al3+、Y3 +、In3+、Sc3+Lanthanide ion groups, and the like.
In the moisture-absorbing material according to an embodiment of the present invention, the ligand is preferably a host molecule forming a clathrate, a chelating agent, or a molecule having a functional group ionically bonded to the metal ion. The host molecule is capable of capturing the metal ion by including the metal ion, coordinating the metal ion with the chelating agent, and bonding the metal ion to a molecule having a functional group that is ionically bonded to the metal ion.
In the moisture-absorbent material according to one embodiment of the present invention, the host molecule is preferably at least one molecule selected from the group consisting of cyclodextrin, a crown compound, cyclophene, azaphene, calixarene, porphyrin, phthalocyanine, schiff base, and derivatives thereof. These host molecules have a ring structure and are capable of recognizing and encapsulating specific metal ions of the type described corresponding to the size, volume, and shape of the internal pores of the ring structure. By encapsulating the metal ions in a hygroscopic polymer material, the salt of the metal ions having high hygroscopicity can be captured by the hygroscopic polymer material, and the hygroscopicity of the hygroscopic polymer material can be improved.
The crown compound is not particularly limited, and examples thereof include crown ethers, benzocrown ethers, dibenzocrown ethers, and azacrown ethers.
The crown ether is not particularly limited, and examples thereof include 12-crown-4, 15-crown-5, and 18-crown-6. In order to obtain a moisture absorbent in which 15-crown-5 is bonded to the moisture absorbent polymer material, for example, 15-crown-5 having a reactive functional group that reacts with the moisture absorbent polymer material can be used. Examples of 15-crown-5 having a reactive functional group that reacts with a hygroscopic polymer material include 2-hydroxymethyl-15-crown-5, 2-aminomethyl-15-crown-5, and 1-aza-15-crown-5. In order to obtain a moisture absorbent in which 18-crown-6 is bonded to the moisture absorbent polymer material, for example, 18-crown-6 having a reactive functional group that reacts with the moisture absorbent polymer material can be used. Examples of 18-crown-6 having a reactive functional group that reacts with a hygroscopic polymer material include 2-hydroxymethyl-18-crown-6, 2-aminomethyl-18-crown-6, (+) - (18-crown-6) -2,11, 12-tetracarboxylic acid, and 1-aza-18-crown-6.
The benzo crown ether is not particularly limited, and examples thereof include benzo-18-crown-6, benzo-21-crown-7, and benzo-24-crown-8.
Examples of the dibenzocrown ether include dibenzo-18-crown-6.
Examples of the azacrown ether include aza-12-crown-4, aza-15-crown-5, and aza-18-crown-6. Examples of aza-15-crown-5 include 1-aza-15-crown-5 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 used by being appropriately selected according to the size of the metal ion to be captured. Specifically, for example, in the case where Li ions and Ca ions are included, the crown ether is preferably 15-crown-5 or aza-15-crown-5. Furthermore, in the case of inclusion of K ions as well as Na ions, the crown ether is preferably 18-crown-6 or aza-18-crown-6.
In the moisture absorbent material according to an embodiment of the present invention, the chelating agent is preferably at least one molecule selected from the group consisting of polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and copolymers of ethylene glycol and propylene glycol, ethylenediamine, bipyridine, ethylenediaminetetraacetic acid, phenanthroline, and derivatives thereof.
In the moisture absorbent material according to an embodiment of the present invention, the molecule having a functional group is preferably at least one or more molecules selected from the group consisting of carboxylic acids, phosphoric acids, sulfonic acids, and amines. Examples of the molecule include poly (meth) acrylic acid, polystyrene sulfonic acid, and polyallylamine.
The moisture-absorbing material according to an embodiment of the present invention preferably further contains a salt of a monovalent, divalent, or trivalent metal ion. The salt is not particularly limited, and examples thereof include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, and aluminum chloride. Among them, the salt is more preferably a deliquescent salt. These salts may be used alone, or two or more of them may be used in combination. By further including the salt of the metal ion in the moisture-absorbing material, the moisture absorption amount and the moisture absorption speed of the moisture-absorbing material can be increased.
(II) hygroscopic Polymer Material
In one embodiment of the present invention, the hygroscopic polymer material may contain a hydrophilic polymer. Examples of the hygroscopic polymer material include a hydrophilic polymer, a mixture containing a hydrophilic polymer, a copolymer containing a hydrophilic polymer, an interpenetrating polymer network structure containing a hydrophilic polymer, and a semi-interpenetrating polymer network structure containing a hydrophilic polymer. The hygroscopic polymer material can absorb moisture in the air by containing a hydrophilic polymer. The moisture-absorbing material according to an embodiment of the present invention contains the moisture-absorbing polymer material. That is, the moisture-absorbent material according to one embodiment of the present invention may be composed of the above-described moisture-absorbent polymer material, or may contain other components within a range that does not adversely affect the effects of the present invention.
In the moisture absorbent material according to an embodiment of the present invention, the moisture absorbent polymer material is more preferably any one of the following (a) to (e):
(a) a hydrophilic polymer;
(b) a mixture of a stimulus-responsive polymer and a hydrophilic polymer, the polymer having an affinity for water reversibly changed in response to an external stimulus;
(c) a copolymer of a stimulus-responsive polymer and a hydrophilic polymer, the polymer having an affinity for water reversibly changed in response to an external stimulus;
(d) a polymer network in which a stimulus-responsive polymer and a hydrophilic polymer, the affinity of which reversibly changes with water in response to an external stimulus, are mutually impregnated; and
(e) the polymer network is formed by semi-interpenetrating a polymer network with a stimulus-responsive polymer and a hydrophilic polymer, the stimulus-responsive polymer and the hydrophilic polymer having reversibly changed affinity for water in response to an external stimulus.
(hydrophilic Polymer)
Examples of the hydrophilic polymer include polymers having a hydrophilic group such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, or an amino group in a side chain or a main chain. More specific examples of the hydrophilic polymer 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, polymaleic acid, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, polyacrylamide alkylsulfonic acid, polydimethylaminopropyl (meth) acrylamide, polymers thereof with (meth) acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylate and the like, a compound of poly (dimethylaminopropyl) (meth) acrylamide and polyvinyl alcohol, a compound of polyvinyl alcohol and poly (meth) acrylic acid, poly (meth) acrylonitrile, 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 polymers. The hydrophilic polymer is more preferably a crosslinked product thereof.
When the hydrophilic polymer is a crosslinked product, examples of the crosslinked product include polymers obtained by polymerizing the following monomers in the presence of a crosslinking agent: monomers such as (meth) acrylic acid, allylamine, vinyl acetate, (meth) acrylamide, N' -dimethyl (meth) acrylamide, 2-hydroxyethyl methacrylate, alkyl (meth) acrylate, maleic acid, vinylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoalkylsulfonic acid, dimethylaminopropyl (meth) acrylamide, and (meth) acrylonitrile.
As the crosslinking agent, conventionally known crosslinking agents may be suitably selected and used, and for example, crosslinking monomers having a polymerizable functional group such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, N' -methylenebis (meth) acrylamide, toluene diisocyanate, divinylbenzene, polyethylene glycol di (meth) acrylate, and the like; glutaraldehyde; a polyol; a polyamine; a polycarboxylic acid; metal ions such as calcium ions and zinc ions. These crosslinking agents may be used alone, or two or more of them may be used in combination.
(stimulus-responsive polymer having reversibly changed affinity for water in response to external stimulus)
The stimulus-responsive polymer is a polymer whose properties reversibly change in response to an external stimulus.
The external stimulus is not particularly limited, and examples thereof include heat, light, an electric field, pH, and the like.
In addition, the reversible change in affinity for water in response to an external stimulus means that a polymer exposed to the external stimulus in response to the external stimulus reversibly changes between hydrophilic and hydrophobic properties.
Among them, a stimulus-responsive polymer whose affinity for water reversibly changes in response to heat, that is, a temperature-responsive polymer, reversibly absorbs moisture in the air and releases the absorbed moisture by changing the temperature using a simple heating device. In this case, the temperature-responsive polymer can be used particularly favorably in a humidifier.
The temperature-responsive polymer is not particularly limited as long as it is a polymer having a lower limit solution temperature (LCST) (hereinafter, may be referred to as "LCST" in the present specification). The polymer having an LCST has hydrophilicity at low temperature, but has hydrophobicity when it is equal to or higher than the LCST. The LCST is a temperature at which a polymer is dissolved in water, is hydrophilic at a low temperature and is dissolved in water, but becomes hydrophobic at a certain temperature or higher and does not dissolve.
More specifically, examples of the temperature-responsive polymer include poly (N-alkyl (meth) acrylamides) such as poly (N-isopropyl (meth) acrylamide), poly (N-propyl (meth) acrylamide), poly (N-methyl (meth) acrylamide), poly (N-ethyl (meth) acrylamide), poly (N-butyl (meth) acrylamide), poly (N-isobutyl (meth) acrylamide), and poly (N-tert-butyl (meth) acrylamide); poly (N-vinyl alkylamides) such as poly (N-vinyl isopropylamide), poly (N-vinyl N-propylamide), poly (N-vinyl N-butylamide), poly (N-vinyl isobutylamide) and poly (N-vinyl t-butylamide); poly (2-alkyl-2-oxazolines) such as poly (N-vinylpyrrolidone), poly (2-ethyl-2-oxazoline), poly (2-isopropyl-2-oxazoline), and poly (2-N-propyl-2-oxazoline); polyvinyl alkyl ethers such as polyvinyl methyl ether and polyvinyl ethyl ether; copolymers of polyethylene oxide and polypropylene oxide; poly (oxyethylene vinyl ethers); cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose, and copolymers of the above polymers. When a cellulose derivative is used as the temperature-responsive polymer, it is not necessary to carry out polymerization, and therefore, the production of the moisture-absorbing material is facilitated. In addition, since the cellulose derivative is safe and biodegradable, it has an advantage of a small environmental load. In the case of using hydroxypropylcellulose as the cellulose derivative, the hydroxypropylcellulose preferably has an average molecular weight of 2,000 to 2000,000 and a degree of substitution of 1 to 3. The temperature-responsive polymer is more preferably a crosslinked product of these polymers.
In one embodiment of the present invention, when the stimulus-responsive polymer and the hydrophilic polymer form a network structure in which the polymers are mutually impregnated, both the stimulus-responsive polymer and the hydrophilic polymer are crosslinked. In one embodiment of the present invention, when the stimulus-responsive polymer and the hydrophilic polymer form a polymer network structure in which the stimulus-responsive polymer and the hydrophilic polymer are semi-impregnated with each other, either one of the stimulus-responsive polymer and the hydrophilic polymer is a crosslinked product.
When the temperature-responsive polymer is a crosslinked product, examples of the crosslinked product include polymers obtained by polymerizing the following monomers or two or more of these monomers in the presence of a crosslinking agent: n-alkyl (meth) acrylamides such as N-isopropyl (meth) acrylamide, N-N-propyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, and N-butyl (meth) acrylamide; n-vinyl alkylamides such as N-vinyl isopropylamide, N-vinyl N-propylamide, N-vinyl N-butylamide, N-vinyl isobutylamide and N-vinyl t-butylamide; vinyl alkyl ethers such as vinyl methyl ether and vinyl ethyl ether; ethylene oxide and propylene oxide; 2-alkyl-2-oxazolines such as 2-ethyl-2-oxazoline, 2-isopropyl-2-oxazoline and 2-n-propyl-2-oxazoline.
As the crosslinking agent, any conventionally known crosslinking agent can be suitably selected and used, and for example, a crosslinkable monomer having a polymerizable functional group such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, N' -methylenebis (meth) acrylamide, toluene diisocyanate, divinylbenzene, or polyethylene glycol di (meth) acrylate; glutaraldehyde; a polyol; a polyamine; a polycarboxylic acid; metal ions such as calcium ions and zinc ions. These crosslinking agents may be used alone, or two or more of them may be used in combination.
Alternatively, when the temperature-responsive polymer is a crosslinked product, the crosslinked product may be a crosslinked product obtained by reacting an uncrosslinked temperature-responsive polymer, for example, the temperature-responsive polymer exemplified above with the crosslinking agent to form a network structure.
Examples of the stimuli-responsive polymer that reversibly changes its affinity for water in response to light include a photoresponsive polymer that changes hydrophilicity or polarity by light, such as an azobenzene derivative or a spiropyran derivative, a copolymer of the photoresponsive polymer and the photoresponsive polymer with at least one of a temperature-responsive polymer and a pH-responsive polymer, a crosslinked product of the photoresponsive polymer, and a crosslinked product of the copolymer.
Examples of the stimuli-responsive polymer that reversibly changes its affinity for water in response to an electric field include polymers having a dissociation group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, or an amino group, polymers that form a complex by electrostatic interaction, hydrogen bonding, or the like, such as a complex of a carboxyl group-containing polymer and an amino group-containing polymer, and crosslinked products thereof.
Examples of the stimuli-responsive polymer that reversibly changes its affinity for water in response to pH include polymers having a dissociation group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, or an amino group, polymers that form a complex by electrostatic interaction, hydrogen bonding, or the like, such as a complex of a carboxyl group-containing polymer and an amino group-containing polymer, and crosslinked products thereof.
The molecular weight of the stimulus-responsive polymer is also not particularly limited, and is preferably 3000 or more in number average molecular weight as determined by Gel Permeation Chromatography (GPC).
((a): hydrophilic Polymer)
The hygroscopic polymer material may be one kind of the hydrophilic polymer, or two or more kinds of the hydrophilic polymers may be mixed and used. In this case, a ligand having affinity for a monovalent, divalent, or trivalent metal ion is bonded to the hydrophilic polymer.
The hydrophilic polymer itself is hydrophilic, and can absorb moisture in the air, and the salt of the metal ion having high hygroscopicity can be captured by bonding the ligand, and the hygroscopicity of the hygroscopic polymer material can be improved. In addition, even when the hydrophilic polymer containing no ligand is used and only the salt of the metal ion is mixed, the salt of the metal ion can be uniformly dispersed by uniformly dispersing the ligand, and therefore, the hygroscopicity can be improved.
The effect of the ligand bonding to the hydrophilic polymer is an effect obtainable in any hygroscopic polymer material containing a hydrophilic polymer. Therefore, similar effects can be obtained also in the cases (b) to (e) described below.
(b) a mixture of a stimulus-responsive polymer and a hydrophilic polymer, the affinity of which reversibly changes with water in response to an external stimulus)
As the hygroscopic polymer material, a stimulus-responsive polymer or a mixture of two or more stimulus-responsive polymers whose affinity for water reversibly changes in response to the external stimulus, and the mixture of (a) can be used. In this case, a ligand having affinity for a monovalent, divalent, or trivalent metal ion is bonded to at least either one of the stimulus-responsive polymer and the hydrophilic polymer.
By using the mixture, the hygroscopic polymer material can reversibly absorb moisture in the air and release the absorbed moisture by changing the temperature of the hygroscopic polymer material due to the property that the affinity of the polymer material for water reversibly changes in response to an external stimulus, for example, using a simple heating device. Further, by bonding the ligand to the hygroscopic polymer material, the salt of the metal ion having high hygroscopicity can be captured, and the hygroscopicity of the hygroscopic polymer material can be improved. Further, as compared with the case where only the salt of the metal ion is mixed by using a hygroscopic polymer material not containing the ligand, the salt of the metal ion can be uniformly dispersed by uniformly dispersing the ligand, and therefore, the hygroscopicity can be improved.
In addition, when only the salt of the metal ion is mixed using a hygroscopic polymer material containing no ligand, there is a problem that the salt of the metal ion leaks out together with the released moisture when the hygroscopic polymer material containing the stimulus-responsive polymer releases the absorbed moisture. Since the salt of the metal ion leaks out, the moisture absorption property of the moisture-absorbing material decreases while the absorption of moisture in the air and the release of the absorbed moisture are repeated. On the other hand, since the ligand holds the metal ion by bonding the ligand to the hygroscopic polymer material, the salt of the metal ion can be prevented from leaking out together with the released water. In addition, in the hygroscopic polymer material, the metal ions are ionized and the donor potential barrier is maintained, so that leakage of the salt of the metal ions can be effectively suppressed.
The effect of the hygroscopic polymer material containing the stimulus-responsive polymer is an effect that can be obtained in any hygroscopic polymer material containing a stimulus-responsive polymer. Accordingly, similar effects can be obtained also in the cases (c) to (e) described below.
The ratio of the stimulus-responsive polymer to the hydrophilic polymer contained in the hygroscopic polymer material is not particularly limited, and the hydrophilic polymer is contained in the stimulus-responsive polymer at a ratio of the weight excluding the weight of the crosslinking agent, more preferably at least 5 wt%, further preferably at least 20 wt%, further preferably at most 1000 wt%, further preferably at most 700 wt%.
(c) a copolymer of a stimulus-responsive polymer and a hydrophilic polymer, the polymer having a reversibly changeable affinity for water in response to an external stimulus)
As the hygroscopic polymer material, the stimulus-responsive polymer or a mixture of two or more stimulus-responsive polymers whose affinity for water reversibly changes in response to an external stimulus, and the copolymer of (a) can be used. In this case, a ligand having affinity for a monovalent, divalent, or trivalent metal ion is bonded to at least either one of the stimulus-responsive polymer and the hydrophilic polymer. Here, the copolymer is not particularly limited as long as it is a polymer including a structural unit constituting the stimulus-responsive polymer and a structural unit constituting the hydrophilic polymer.
The ratio of the structural unit constituting the stimulus-responsive polymer and the structural unit constituting the hydrophilic polymer contained in the hygroscopic polymer material to all the structural units is not particularly limited, but the structural unit constituting the hydrophilic polymer is contained in the stimulus-responsive polymer at a ratio of more preferably 30 mol% or more, further preferably 40 mol% or more, further preferably 80 mol% or less, and further preferably 50 mol% or less.
(d) a polymer network in which a stimulus-responsive polymer and a hydrophilic polymer, the affinity of which reversibly changes with water in response to an external stimulus, are mutually immersed
As the hygroscopic polymer material, the stimulus-responsive polymer or a mixture of two or more stimulus-responsive polymers, and the mutually-impregnated polymer network of (a) can be used. Here, the mutually-impregnated polymer network structure refers to a structure in which different types of polymers are crosslinked polymers, and the crosslinked networks of the respective polymers are entangled with each other in a state of being not chemically bonded but independently present. That is, the mutually-impregnated polymer network structure refers to a structure in which the hydrophilic polymer and the stimulus-responsive polymer are both crosslinked polymers, and the crosslinked network of the hydrophilic polymer and the crosslinked network of the stimulus-responsive polymer are entangled with each other in a state in which they are not chemically bonded but exist independently. When the hydrophilic polymer or the stimulus-responsive polymer is a mixture, at least one of the hydrophilic polymer and the stimulus-responsive polymer in the mixture may be a polymer network structure in which the hydrophilic polymer and the stimulus-responsive polymer are mutually immersed. By using the mutually-impregnated polymer network structure, the affinity for water in response to an external stimulus is more clearly and reversibly changed than in the case of using a mixture or copolymer of the hydrophilic polymer and the stimulus-responsive polymer. Therefore, by applying the external stimulus, the moisture in the air can be absorbed and the absorbed moisture can be released more efficiently, and therefore, the moisture absorber can be used particularly suitably in a humidifier.
The ratio of the stimulus-responsive polymer to the hydrophilic polymer contained in the hygroscopic polymer material is not particularly limited, and the hydrophilic polymer is contained in the stimulus-responsive polymer at a ratio of the weight excluding the weight of the crosslinking agent, more preferably at least 5 wt%, further preferably at least 20 wt%, further preferably at most 1000 wt%, further preferably at most 700 wt%.
(e) a polymer network in which a stimulus-responsive polymer and a hydrophilic polymer, the affinity of which reversibly changes with water in response to an external stimulus, are semi-interpenetrating
As the hygroscopic polymer material, the stimulus-responsive polymer or a mixture of two or more stimulus-responsive polymers, and the semi-polymer of (a) may be impregnated into each other to form a polymer network. Here, the semi-interpenetrating polymer network structure refers to a structure in which one of different kinds of polymers is a crosslinked polymer, the other is a linear polymer or a non-crosslinked polymer, and the respective polymers are entangled with each other in a state of being present independently without being chemically bonded. That is, the stimulus-responsive polymer or the mixture of two or more stimulus-responsive polymers and the hydrophilic polymer semi-interpenetrating polymer network structure refers to a structure in which either one of the hydrophilic polymer and the stimulus-responsive polymer is a crosslinked polymer and the other is a non-crosslinked polymer, and the stimulus-responsive polymer and the hydrophilic polymer are entangled with each other in a state in which they are not chemically bonded but are independently present. In the case where the hydrophilic polymer or the stimulus-responsive polymer is a mixture, at least one of the hydrophilic polymer and the stimulus-responsive polymer in the mixture may form a semi-interpenetrating polymer network. By using the semi-interpenetrating polymer network, the affinity for water in response to an external stimulus is more clearly and reversibly changed than in the case of using a mixture or copolymer of the hydrophilic polymer and the stimulus-responsive polymer. Accordingly, the moisture in the air can be absorbed and the absorbed moisture can be released more efficiently by applying the external stimulus, and thus the moisture absorber can be used particularly suitably in a humidifier.
The ratio of the stimulus-responsive polymer to the hydrophilic polymer contained in the hygroscopic polymer material is not particularly limited, and the hydrophilic polymer is contained in the stimulus-responsive polymer at a ratio of the weight excluding the weight of the crosslinking agent, more preferably at least 5 wt%, further preferably at least 20 wt%, further preferably at most 1000 wt%, further preferably at most 700 wt%.
(III) moisture absorbent Material
In the moisture-absorbing material according to an embodiment of the present invention, a ratio of the ligand contained in the moisture-absorbing polymer material to a total structural unit of a polymer contained in the moisture-absorbing polymer material is preferably 10 mol% to 80 mol%, more preferably 30 mol% to 80 mol%, and still more preferably 40 mol% to 70 mol%. If the ligand content is 40 mol% or more, the content of metal ions in the hygroscopic material also increases, and therefore the hygroscopicity is improved. If the ligand content is 70 mol% or less, the release of absorbed water is not affected when the stimulus-responsive polymer is used, and therefore, it is preferable. The term "contained in the hygroscopic polymer material" as used herein means that the material is present in the hygroscopic polymer material and may be bonded to the hygroscopic polymer material or not.
In the moisture absorbent material according to one embodiment of the present invention, at least a part of the ligand is bonded to the moisture absorbent polymer 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 to 80 mol%, and still more preferably 40 to 70 mol%. If the ligand content is 40 mol% or more, the content of metal ions in the hygroscopic material also increases, and therefore the hygroscopicity is improved. If the ligand content is 70 mol% or less, the release of absorbed water is not affected when the stimulus-responsive polymer is used, and therefore, it is preferable.
The shape of the moisture-absorbent material according to an embodiment of the present invention is not particularly limited, and may be a plate, a sheet, a film, or a particle. The shape of the particulate moisture-absorbing material is not particularly limited, and may be, for example, a substantially spherical shape or a plate-like shape. The size of the moisture absorbing material according to the present invention is not particularly limited, and when the moisture absorbing material is used in a humidifier, the size may be appropriately selected according to the structure of the humidifier.
The hygroscopic polymer material is preferably dried by, for example, drying under reduced pressure (vacuum), heat drying, natural drying, or a combination thereof, and more preferably dried by drying under reduced pressure or heat drying. The hygroscopic polymer material can be dried to form a dry hygroscopic polymer material having a dense network structure, because fine pores are formed when the solvent used for polymerization is sublimated to the outside by drying under reduced pressure or by heat drying. Since the hygroscopic polymer material having a dense network structure has a large area in contact with air, the ratio of the amount of moisture absorbed in air increases. In addition, the hygroscopic polymer material having a dense network structure can suppress leakage of the salt of the metal ion by entanglement of molecular chains close to each other. In addition, the hygroscopic polymer material having a relatively dense network structure can maintain the equilibrium state after the salt of the metal ion is released together with the released water because the presence of the functional group of the hygroscopic polymer material that is not bonded to the ligand keeps the charge neutralization in the hygroscopic polymer material, both when moisture in the air is absorbed and when water is released by a stimulus such as heating.
The degree of reduced pressure when drying is performed by the reduced pressure drying is preferably 10 to 100Pa, and more preferably 20 to 50 Pa.
The reduced pressure drying is more preferably freeze drying performed after freezing the water-absorbent polymer material. The hygroscopic polymer material is frozen and then dried under reduced pressure, so that fine pores are formed in the hygroscopic polymer material when the solvent used for polymerization is sublimated to the outside, and a dried body of the hygroscopic polymer material having a more dense network structure can be formed. The freezing temperature is preferably-60 ℃ to-20 ℃, more preferably-60 ℃ to-30 ℃. The drying time depends on the amount of the sample, and 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.
In one embodiment of the present invention, the dried body of the hygroscopic polymer material does not need to completely remove moisture from the hygroscopic polymer material, and may contain moisture if it can absorb moisture in the air. Therefore, the moisture content of the dried product of the hygroscopic polymer material is not particularly limited if the dried product can absorb moisture in the air, and is, for example, preferably 10 to 30% by weight, and more preferably 20 to 25% by weight. Here, the water content is a ratio of water to a dry weight of the hygroscopic polymer material.
The description relating to the dried product is also applicable to the moisture-absorbing polymer material, and the same is true of the moisture-absorbing material.
[ second embodiment: method for producing moisture-absorbing Material
A method for producing a moisture-absorbing material according to an embodiment of the present invention is a method for producing a moisture-absorbing material including: the hygroscopic material contains a hygroscopic polymer material containing a hydrophilic polymer, and a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded to the hygroscopic polymer material.
A method for producing a moisture-absorbent material according to an embodiment of the present invention may include at least the steps of: a hygroscopic polymer material production step of producing a hygroscopic polymer material that contains a hydrophilic polymer and to which a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded; and a drying step of drying the hygroscopic polymer material obtained in the hygroscopic polymer material production step. The drying step may further include a pulverization step of pulverizing the hygroscopic polymer material dried in the drying step.
Hereinafter, each step constituting the method for producing a moisture-absorbent material according to an embodiment of the present invention will be described. However, the description of the moisture absorbent material will be omitted in the same manner as the description of the moisture absorbent material.
(Process for producing hygroscopic Polymer Material)
The hygroscopic polymer material production step is not particularly limited if it is a step capable of producing the hygroscopic polymer material, and the hygroscopic polymer material can be produced by, for example, the following method.
[1] A method comprising the steps of: (i) reacting a monomer constituting the hydrophilic polymer with the ligand to bond at least a part of the ligand to the monomer constituting the hydrophilic polymer; and (ii) polymerizing the ligand-bonded monomer obtained in the step (i).
[2] A method comprising the steps of: (ii) a step (i) of polymerizing a monomer constituting the hydrophilic polymer to synthesize the hydrophilic polymer or preparing a commercially available hydrophilic polymer; and (ii) reacting the hydrophilic polymer with the ligand to bond at least a part of the ligand to the hydrophilic polymer.
[3] A method comprising the steps of: (ii) reacting a monomer constituting the stimulus-responsive polymer with the ligand to bond at least a part of the ligand to the monomer constituting the stimulus-responsive polymer; (ii) synthesizing the stimulus-responsive polymer to which the ligand is bonded by polymerizing the monomer to which the ligand is bonded, which is obtained in the step (i); and (iii) mixing the stimulus-responsive polymer obtained in the step (ii) with the hydrophilic polymer obtained by the method of [1] or [2 ].
[4] A method comprising the steps of: (ii) polymerizing a monomer constituting the stimulus-responsive polymer to synthesize the stimulus-responsive polymer or preparing a commercially available stimulus-responsive polymer; (ii) reacting the stimulus-responsive polymer with the ligand to bond at least a part of the ligand to the stimulus-responsive polymer, thereby obtaining the stimulus-responsive polymer to which the ligand is bonded; and (iii) mixing the stimulus-responsive polymer obtained in the step (ii) with the hydrophilic polymer obtained by the method of [1] or [2 ].
[5] A method comprising the steps of: (ii) a step (i) of reacting the monomer constituting the hydrophilic polymer, the monomer constituting the stimulus-responsive polymer, and the ligand to bond at least a part of the ligand to the monomer constituting the hydrophilic polymer and/or the monomer constituting the stimulus-responsive polymer, respectively; and (ii) copolymerizing the monomer constituting the hydrophilic polymer obtained in the step (i) with the monomer constituting the stimulus-responsive polymer.
[6] A method comprising the steps of: a step (i) of obtaining a copolymer by copolymerizing a monomer constituting the hydrophilic polymer and a monomer constituting the stimulus-responsive polymer; and (ii) reacting the copolymer obtained in the step (i) with the ligand to bond at least a part of the ligand to the copolymer.
[7] A method comprising the steps of: (ii) reacting a monomer constituting the stimulus-responsive polymer with the ligand to bond at least a part of the ligand to the monomer constituting the stimulus-responsive polymer; (ii) polymerizing and crosslinking the monomer constituting the stimulus-responsive polymer obtained in the step (i) to form a crosslinked network (a) of the crosslinked product of the stimulus-responsive polymer;
(iii) reacting a monomer constituting the hydrophilic polymer with the ligand to bond at least a part of the ligand to the monomer constituting the hydrophilic polymer; (iv) a step (iv) of polymerizing and crosslinking the monomer constituting the hydrophilic polymer obtained in the step (iii) in the presence of the crosslinked network (a) to form a polymer network structure composed of the crosslinked network (a) and the crosslinked network (b) of the crosslinked product of the hydrophilic polymer, which are impregnated with each other.
[8] A method comprising the steps of: a step (i) of forming a crosslinked network (a) of a crosslinked product of the stimulus-responsive polymer by polymerizing and crosslinking a monomer constituting the stimulus-responsive polymer;
a step (ii) of forming a polymer network structure composed of a crosslinked network (a) and a crosslinked network (b) of a crosslinked product of the hydrophilic polymer by polymerizing and crosslinking a monomer constituting the hydrophilic polymer in the presence of the crosslinked network (a); and (iii) reacting the hygroscopic polymer material having the mutually-impregnated polymer network structure obtained in the step (ii) with the ligand to bond at least a part of the ligand to the hygroscopic polymer material.
[9] A method comprising the steps of: (ii) reacting a monomer constituting the stimulus-responsive polymer with the ligand to bond at least a part of the ligand to the monomer constituting the stimulus-responsive polymer; (ii) polymerizing and crosslinking the monomer constituting the stimulus-responsive polymer obtained in the step (i) to form a crosslinked network (a) of a crosslinked product of the stimulus-responsive polymer;
(iii) reacting a monomer constituting the hydrophilic polymer with the ligand to bond at least a part of the ligand to the monomer constituting the hydrophilic polymer; (iv) polymerizing the monomer constituting the hydrophilic polymer obtained in the step (iii) in the presence of the crosslinked network (a), thereby forming a semi-interpenetrating polymer network structure composed of the crosslinked network (a) and the non-crosslinked hydrophilic polymer.
[10] A method comprising the steps of: a step (i) of forming a crosslinked network (a) of a crosslinked product of the stimulus-responsive polymer by polymerizing and crosslinking a monomer constituting the stimulus-responsive polymer;
a step (ii) of polymerizing a monomer constituting the hydrophilic polymer in the presence of the crosslinked network (a) to form a semi-interpenetrating polymer network structure composed of the crosslinked network (a) and the non-crosslinked hydrophilic polymer; and (iii) reacting the hygroscopic polymer material having the semi-interpenetrating polymer network structure formed thereon obtained in the step (ii) with the ligand to bond at least a part of the ligand to the hygroscopic polymer material.
[11] A method comprising the steps of: (ii) reacting a monomer constituting the stimulus-responsive polymer with the ligand to bond at least a part of the ligand to the monomer constituting the stimulus-responsive polymer; (ii) polymerizing the monomer constituting the stimulus-responsive polymer obtained in the step (i) to produce a non-crosslinked stimulus-responsive polymer;
(iii) reacting a monomer constituting the hydrophilic polymer with the ligand to bond at least a part of the ligand to the monomer constituting the hydrophilic polymer; (iv) polymerizing and crosslinking the monomer constituting the hydrophilic polymer obtained in the step (ii) in the presence of the non-crosslinked stimulus-responsive polymer to form a semi-interpenetrating polymer network structure composed of the non-crosslinked stimulus-responsive polymer and the crosslinked network (b) of the crosslinked product of the hydrophilic polymer.
[12] A method comprising the steps of: (ii) a step (i) of polymerizing a monomer constituting the stimulus-responsive polymer to produce a non-crosslinked stimulus-responsive polymer; (ii) polymerizing and crosslinking a monomer constituting the hydrophilic polymer in the presence of the non-crosslinked stimulus-responsive polymer obtained in step (i) to form a semi-interpenetrating polymer network structure composed of the non-crosslinked stimulus-responsive polymer and a crosslinked network (b) of the crosslinked product of the hydrophilic polymer; and (iii) reacting the hygroscopic polymer material having the semi-interpenetrating polymer network structure formed thereon obtained in the step (ii) with the ligand to bond at least a part of the ligand to the hygroscopic polymer material.
In the methods of [3] and [4], the hydrophilic polymer to which the ligand is bonded and the stimulus-responsive polymer to which the ligand is bonded are mixed, but a polymer to which the ligand is not bonded may be used as either one of the hydrophilic polymer and the stimulus-responsive polymer.
In the method of [7], the hydrophilic polymer to which the ligand is bonded and the stimulus-responsive polymer to which the ligand is bonded are formed to be impregnated into a polymer network structure, but a polymer to which the ligand is not bonded may be used as either one of the hydrophilic polymer and the stimulus-responsive polymer.
In the methods of [1] to [12], the polymerization method for polymerizing the monomer is not particularly limited, and radical polymerization, ionic polymerization, polycondensation, ring-opening polymerization, and the like can be suitably used. The solvent used for polymerization may be appropriately selected depending on the monomer, and for example, water, phosphate buffer, Tris buffer, acetate buffer, methanol, ethanol, or the like can be suitably used.
The polymerization initiator is also not particularly limited, and, for example, persulfate salts such as ammonium persulfate and sodium persulfate; hydrogen peroxide; peroxides such as t-butyl hydroperoxide and cumene hydroperoxide; azobisisobutyronitrile, benzoyl peroxide, and the like. Among these polymerization initiators, particularly, initiators exhibiting oxidizing properties such as persulfate and peroxide can be used as a redox initiator with, for example, sodium bisulfite, N, N, N ', N' -tetramethylethylenediamine, and the like. Alternatively, light, radiation, or the like may be used as the initiator.
The polymerization temperature is not particularly limited, but is usually 5 to 80 ℃. The polymerization time is also not particularly limited, but is usually 4 to 48 hours.
The concentration of the monomer, the crosslinking agent, and the like in the polymerization is not particularly limited as long as the stimulus-responsive polymer, the hydrophilic polymer, or the crosslinked product thereof is obtained. Further, the concentration of the polymerization initiator is also not particularly limited as long as it is appropriately selected.
In the methods of [7] to [12], the method of polymerizing and crosslinking a monomer to form a crosslinked network of the stimulus-responsive polymer or the crosslinked product of the hydrophilic polymer may be a method of polymerizing a monomer in the presence of a crosslinking agent, or a method of polymerizing a monomer to form a polymer and then crosslinking the polymer with a crosslinking agent.
In the step (iv) of the above-mentioned [7], [9] and [11], the polymerization conditions or crosslinking conditions under which no crosslinking is formed between the polymers or crosslinked products thereof formed in the step (ii) may be appropriately selected. In the step (iii) of the above-mentioned [8], [10] and [12], the polymerization conditions or crosslinking conditions under which no crosslinking is formed between the polymers or the crosslinked products thereof formed in the step (i) may be appropriately selected.
In the methods of [1] to [12], the monomer constituting the stimulus-responsive polymer, the monomer constituting the hydrophilic polymer, and the crosslinking agent are as described in the above (I).
In the methods of [7] to [12], when the stimulus-responsive polymer or the hydrophilic polymer is initially a polymer such as a cellulose derivative or a polysaccharide, "polymerizing and crosslinking a monomer constituting the stimulus-responsive polymer" is rewritten as "crosslinking the stimulus-responsive polymer," and "polymerizing and crosslinking a monomer constituting the hydrophilic polymer" is rewritten as "crosslinking the hydrophilic polymer.
Further, in the methods of [7] to [12], the hydrophilic polymer or the crosslinked product thereof is produced in the presence of the obtained stimulus-responsive polymer or the crosslinked product thereof after the stimulus-responsive polymer or the crosslinked product thereof is produced, but the stimulus-responsive polymer or the crosslinked product thereof may be produced in the presence of the obtained hydrophilic polymer or the crosslinked product thereof after the hydrophilic polymer or the crosslinked product thereof is produced.
Further, in the methods of [7] to [12], the mutually-immersed polymer network structure or the semi-mutually-immersed polymer network structure is produced by two steps of: producing the hydrophilic polymer or the crosslinked product thereof in the presence of the obtained stimulus-responsive polymer or the crosslinked product thereof after producing the stimulus-responsive polymer or the crosslinked product thereof; however, if polymerization conditions or crosslinking conditions are selected such that no crosslinking is formed between the stimulus-responsive polymer or the crosslinked product thereof and the hydrophilic polymer or the crosslinked product thereof, the polymerization conditions or the crosslinking conditions can be performed simultaneously in one stage. For example, if a combination of a polymerization method and a crosslinking agent used for producing the hydrophilic polymer or the crosslinked product thereof, and a combination of a polymerization method and a crosslinking agent used for producing the hydrophilic polymer or the crosslinked product thereof are different, the hygroscopic polymer material can be produced by a single step.
(drying Process)
In the drying step, the hygroscopic polymer material obtained in the hygroscopic polymer material production step is dried to obtain a dried body of the hygroscopic polymer material.
The method for drying the moisture-absorbing polymer material is not particularly limited, and conventionally known methods can be suitably used. Examples of the method for drying the moisture-absorbing polymer material include drying by heating, drying under reduced pressure, freeze drying, and a solvent substitution method.
(grinding step)
The dried body of the hygroscopic polymer material obtained in the drying step is pulverized in the pulverizing step as necessary.
The method of pulverization is not particularly limited, and for example, a mechanical pulverizer such as a rotor, a ball mill, a jet mill, or the like can be used to pulverize the dried body of the hygroscopic polymer material and, if necessary, further classify the pulverized body into a particulate hygroscopic material.
The particulate moisture absorbent material may be produced by the following method: in the process of producing a hygroscopic polymer material, fine particles of the hygroscopic polymer material are synthesized by emulsion polymerization.
[ third embodiment: humidifier
The moisture absorbent material according to the present invention, particularly the moisture absorbent material containing the hydrophilic polymer and the stimuli-responsive polymer, can reversibly absorb moisture in the air and release the absorbed moisture, and therefore is particularly suitable for use in a humidity controller, and a humidity controller using the moisture absorbent material can efficiently perform humidity control without using supercooling or large heat. Therefore, a humidity conditioner using the moisture absorbing material according to one embodiment of the present invention is also included in the present invention. A humidifier according to an embodiment of the present invention will be described below. A humidity conditioner according to an embodiment of the present invention includes: a hygroscopic material containing a hygroscopic polymer material containing a hydrophilic polymer and a stimulus-responsive polymer, wherein a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded to the hygroscopic polymer material; and a stimulus applying unit for applying an external stimulus for reducing the affinity of the stimulus-responsive polymer for water. Here, the moisture absorbent material preferably further comprises a salt of a monovalent, divalent, or trivalent metal ion. The moisture absorbent material is not described in detail with respect to the same contents as those described in the [ first embodiment ].
A humidifier according to an embodiment of the present invention includes a humidifier main body having an intake port and an exhaust port. The humidity conditioner main body is provided with: a plurality of humidity control units on which the moisture absorbent material of the present invention is carried; a humidity control region in which the humidity control unit absorbs moisture in the air; a dehydration region in which the humidity control unit that has absorbed moisture in the air releases the absorbed moisture as water; a drain tank that stores the released water; and a blower fan for sucking air to be moisture-absorbed from the air inlet and discharging the air having been moisture-absorbed from the air outlet. In the present embodiment, the following humidity control materials are used as the humidity control material: the humidity control material contains a hygroscopic polymer material containing a hydrophilic polymer and a stimulus-responsive polymer whose affinity for water reversibly changes in response to an external stimulus, and a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded to the hygroscopic polymer material.
The plurality of humidity control units are movable between the humidity control area and the dewatering area. The dehydration region is provided with a stimulus applying unit for applying an external stimulus for reducing the affinity of the stimulus-responsive polymer for water. When the stimulus-responsive polymer is, for example, a temperature-responsive polymer, the stimulus applying unit is, for example, a heater.
The air (humid air) drawn by the humidity conditioner comes into contact with the moisture absorbent material of the humidity conditioning unit while passing through the humidity conditioning area. The moisture absorbing material, which is hydrophilic at room temperature, absorbs moisture in the air (humid air), whereby the humid air is absorbed in passing through the humidity control area, and the air (dry air) having been absorbed in moisture is discharged from the air outlet.
The humidity control unit that has absorbed moisture in the air (moist air) moves from the humidity control area into the dewatering area. In the dewatering area, the humidity control unit that moves to the dewatering area applies an external stimulus to the moisture absorbing material by the stimulus applying section, thereby rendering the moisture absorbing material hydrophobic. As a result, the moisture absorbed by the moisture-absorbing material is released as water from the moisture-absorbing material. And, the released water is discharged to the drain tank.
In this case, in the humidity conditioner according to an embodiment of the present invention, since the ligand is bonded to the hygroscopic polymer material of the moisture absorbent material, the ligand holds the metal ion, and thus the salt of the metal ion can be prevented from leaking out together with the released water. Accordingly, even when the humidity control unit is repeatedly moved between the humidity control region and the dehydration region to repeat the absorption of moisture in the air and the release of the absorbed moisture by the moisture absorbent material, the decrease in the moisture absorption property of the moisture absorbent material can be suppressed.
The present invention is not limited to the above embodiments, and various modifications can be made within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the technical scope of the present invention. Further, by combining the technical means disclosed in the respective embodiments, new technical features can be formed.
[ conclusion ]
A moisture-absorbing material according to a first aspect of the present invention is a moisture-absorbing material containing a moisture-absorbing polymer material, and includes: the hygroscopic polymer material contains a hydrophilic polymer, and a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded to the hygroscopic polymer material.
According to the above configuration, the following effects can be obtained: a salt capable of capturing the metal ion having a high hygroscopicity, and a moisture-absorbing material capable of preventing leakage of deliquescent liquid derived from the salt and having a more excellent hygroscopicity.
A moisture-absorbent material according to a second aspect of the present invention is the moisture-absorbent material according to the first aspect, further comprising: the ligand is a host molecule that forms a clathrate, a chelating agent, or a molecule having a functional group that ionically bonds with the metal ion.
According to the above configuration, the salt of the metal ion having high hygroscopicity can be captured by the hygroscopic polymer material, and the hygroscopicity of the hygroscopic polymer material can be improved.
A moisture-absorbing material according to a third aspect of the present invention is the moisture-absorbing material according to the second aspect, further including: the host molecule is at least one molecule selected from the group consisting of cyclodextrin, a crown compound, cyclophene, azacyclophene, calixarene, porphyrin, phthalocyanine, schiff base, and derivatives thereof.
According to the above configuration, the salt of the metal ion having high hygroscopicity can be captured by the hygroscopic polymer material, and the hygroscopicity of the hygroscopic polymer material can be improved.
A moisture-absorbing material according to a fourth aspect of the present invention is the moisture-absorbing material according to the second aspect, further including: the chelating agent is at least one molecule selected from the group consisting of polyalkylene glycol, ethylenediamine, bipyridine, ethylenediamine tetraacetic acid, phenanthroline, and derivatives thereof.
According to the above configuration, the salt of the metal ion having high hygroscopicity can be captured by the hygroscopic polymer material, and the hygroscopicity of the hygroscopic polymer material can be improved.
A moisture-absorbent material according to a fifth aspect of the present invention is the moisture-absorbent material according to the second aspect, further comprising: the molecule having a functional group is at least one or more molecules selected from the group consisting of carboxylic acid, phosphoric acid, sulfonic acid, and amine.
According to the above configuration, the salt of the metal ion having high hygroscopicity can be captured by the hygroscopic polymer material, and the hygroscopicity of the hygroscopic polymer material can be improved.
A moisture-absorbing material according to a sixth aspect of the present invention is the moisture-absorbing material according to any one of the first to fifth aspects, further including: the hygroscopic polymer material is any one of the following (a) to (e):
(a) a hydrophilic polymer;
(b) a mixture of a stimulus-responsive polymer and a hydrophilic polymer, the polymer having an affinity for water reversibly changed in response to an external stimulus;
(c) a copolymer of a stimulus-responsive polymer and a hydrophilic polymer, the polymer having an affinity for water reversibly changed in response to an external stimulus;
(d) a polymer network in which a stimulus-responsive polymer and a hydrophilic polymer, the affinity of which reversibly changes with water in response to an external stimulus, are mutually impregnated; and
(e) the polymer network is formed by semi-interpenetrating a polymer network with a stimulus-responsive polymer and a hydrophilic polymer, the stimulus-responsive polymer and the hydrophilic polymer having reversibly changed affinity for water in response to an external stimulus.
According to the above configuration (a), the hydrophilic polymer is hydrophilic and can absorb moisture in the air, and in addition, the ligand is bonded, whereby the salt of the metal ion having high hygroscopicity can be captured, and the hygroscopicity of the hygroscopic polymer material can be improved. In addition, as compared with the case where only the salt of the metal ion is mixed using a hydrophilic polymer not containing the ligand, the salt of the metal ion can be uniformly dispersed by uniformly dispersing the ligand, and therefore, the hygroscopicity can be improved.
According to the above configurations (b) to (e), in addition to the above configurations, in the case where only the salt of the metal ion is mixed using the stimuli-responsive polymer not containing the ligand, there is a problem that the salt of the metal ion leaks out together with the released moisture when the moisture absorbed by the stimuli-responsive polymer is released. Since the salt of the metal ion leaks out, the moisture absorption of the moisture-absorbing material decreases while the absorption of moisture in the air and the release of the absorbed moisture are repeated. On the other hand, since the ligand holds the metal ion by bonding the stimulus-responsive polymer to the ligand, the salt of the metal ion can be prevented from leaking out together with the released water.
A moisture-absorbing material according to a seventh aspect of the present invention is the moisture-absorbing material according to any one of the first to sixth aspects, further including: 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 to 80 mol%.
According to the above configuration, the moisture absorption property of the moisture absorbent material can be improved, and it is preferable that the stimulus-responsive polymer is used, since the release of absorbed moisture is not affected.
A moisture-absorbing material according to an eighth aspect of the present invention is the moisture-absorbing material according to any one of the first to eighth aspects, further including: further comprising salts of monovalent, divalent, or trivalent metal ions.
According to the above configuration, the moisture absorption property of the moisture absorbent material can be improved.
Examples 1 to 3 and comparative example 1
<Example 1: Alg-PEG (CaCl)2Synthesis of/LiCl)/HPC semi-interpenetrating Polymer networks>
Dissolving sodium alginate (Alg) 100mg and polyethylene glycol diglycidyl ether (PEGDE) 10 wt% relative to AlgIn 100ml of ultrapure water. The aqueous solution obtained was heated at 70 ℃ for 11 hours. The heated aqueous solution was mixed with an aqueous solution of hydroxypropyl cellulose (HPC) (an aqueous solution prepared by dissolving HPC (hydroxypropyl cellulose 150 to 400cP, manufactured by wako pure chemical industries, ltd.) in 100ml of ultrapure water). To the obtained mixed solution was added CaCl at a concentration of 0.5M each2Aqueous LiCl solution (200 ml) and left to stand for 24 hours, thereby obtaining a polyethylene glycol (PEG) -bonded alginic acid and HPC semi-interpenetrating polymer network with CaCl captured therein2Polymer gel of/LiCl (Alg-PEG (CaCl)2/LiCl)/HPC semi-interpenetrating polymer networks). Freezing the obtained polymer gel at-30 deg.C, and drying under reduced pressure of 20Pa for 36 hr to obtain polymer network structure with CaCl trapped in half-immersed Alg-PEG/HPC2Dried polymer gel of LiCl (moisture absorbent material 1). The ligand accounts for about 5 mol% of the total structural units of the polymer contained in the moisture absorbent material 1.
< example 2>
The procedure of example 1 was repeated except that the amount of PEGDE added to alginic acid (Alg) sodium was 20 wt% based on Alg to obtain Alg-PEG/HPC semi-interpenetrating polymer network with CaCl trapped therein2Dried polymer gel of LiCl (moisture absorbent 2). The ligand is present in a proportion of about 10 mol% with respect to the total structural units of the polymer contained in the moisture absorbent material 2.
< example 3>
The procedure of example 1 was repeated except that the amount of PEGDE added to alginic acid (Alg) sodium was changed to 30 wt% based on Alg to obtain Alg-PEG/HPC semi-interpenetrating polymer network with CaCl trapped therein2Dried polymer gel of LiCl (moisture absorbent 3). The ratio of the ligand to the total structural units of the polymer contained in the moisture absorbent material 3 is about 15 mol%.
< comparative example 1: synthesis of a semi-interpenetrating Alg/HPC Polymer network >
The amount of PEGDE added to alginic acid (Alg) sodium was 0, andexample 1 the same procedure was followed to obtain a dried body in which Alg/HPC was half-impregnated into a polymer network and CaCl2Mixture of/LiCl (comparative hygroscopic material 1).
<The half-interpenetrated Alg/HPC polymer networks and Alg-PEG (CaCl)2Moisture absorption characteristics of/LiCl)/HPC semi-interpenetrated polymeric network>
The moisture-absorbing materials 1 to 3 and the comparative moisture-absorbing material 1 were left standing under the constant temperature and humidity conditions of 25 ℃ and 80% RH, and the change in weight was measured over time, thereby studying the moisture-absorbing characteristics thereof.
The time-moisture absorption rate is shown in fig. 1. In fig. 1, the vertical axis represents the water content (in fig. 1, the moisture content is referred to as "Amount of moisture absorbed", in other words, the Amount of moisture absorbed in the air, the unit is g/g-dry product (in fig. 1, the unit is referred to as "g/g-dry polymer)"), and the horizontal axis represents the time (unit is minutes). As shown in fig. 1, the higher the ratio of PEG bonded to Alg, the higher the moisture absorption rate. The reason for this is that: when the amount of PEG is large, the amount of Ca ions and Li ions coordinated increases.
Example 4 and comparative example 2
<Example 4: Alg-CE (CaCl)2LiCl) Synthesis>
Sodium alginate (Alg) (1 g) was dissolved in 100ml of ultrapure water. To the obtained Alg aqueous solution, 735mg of dichloroethane (EDC) and 437mg of N-hydroxysuccinimide (NHS) were added and stirred for 30 minutes to react with 50 mol% of carboxyl groups in Alg, thereby preparing an EDC/NHS-activated Alg aqueous solution. Next, an aqueous CE solution prepared by dissolving 690mg of 2-aminomethyl-15-crown-5 (CE) in 10ml of ultrapure water was added dropwise to the EDC/NHS-activated Alg aqueous solution and stirred for 8 hours to obtain an aqueous Alg-CE-containing solution. The aqueous solution comprising Alg-CE was purified by: the cellulose membrane is dialyzed into ultrapure water using a cellulose dialysis membrane, and low molecules smaller than the molecular weight cut-off in the solution are removed by passive diffusion. Thereafter, the purified Alg-CE was dissolved in ultrapure water to prepare an Alg-CE aqueous solution. To the Alg-CE aqueous solution was added CaCl at a concentration of 0.5M each2LiCl aqueous solution 200ml and standing for 20 hours to obtain the product with CaCl trapped in CE-bonded alginic acid2Polymer gel of/LiCl (Alg-CE (CaCl)2/LiCl)). The obtained polymer gel was frozen at-30 ℃ and dried under a reduced pressure of 20Pa for 36 hours to obtain a dried product (moisture-absorbing material 4). The ligand is present in a proportion of about 50 mol% with respect to the total structural units of the polymer contained in the moisture absorbent material 4.
< comparative example 2>
Sodium alginate (Alg) (1 g) was dissolved in 100ml of ultrapure water. To the obtained Alg aqueous solution was added CaCl at a concentration of 0.5M each2LiCl aqueous solution 200ml and left for 30 hours, obtained as Alg with CaCl2Polymer gel of a mixture of/LiCl. Freezing the obtained polymer gel at-30 deg.C, and drying under reduced pressure of 20Pa for 36 hr to obtain Alg and CaCl2Dried polymer gel of LiCl mixture (comparative hygroscopic material 2).
<Alg and Alg-CE (CaCl)2LiCl) moisture absorption characteristics>
The moisture absorption characteristics thereof were investigated by standing the moisture-absorbent material 4 and the comparative moisture-absorbent material 2 under constant temperature and humidity conditions at a temperature of 25 ℃ and a humidity of 80% RH and measuring the change in weight over time.
The time-moisture absorption rate is shown in fig. 2. In fig. 2, the vertical axis represents the water content (in fig. 2, the water content is referred to as "Amount of moisture absorbed in the air, in other words, the Amount of moisture absorbed in the air, the unit is g/g-dry body (in fig. 2, the unit is referred to as" g/g-dry polymer ")), and the horizontal axis represents the time (the unit is minutes). As shown in fig. 2, the moisture absorption rate was improved in the moisture absorbent material 4 in which Alg was bonded to CE and the comparative moisture absorbent material 2 in which Alg was not bonded to CE. The reason for this is that: the CECa ion and the Li ion are included.
Industrial applicability
The moisture-absorbing material of the present invention is very useful as a moisture-absorbing and dehydrating material, and can be suitably used in a humidifier.

Claims (8)

1. A moisture-absorbing material comprising a moisture-absorbing polymer material,
the hygroscopic polymer material contains a hydrophilic polymer,
a ligand having an affinity for a monovalent, divalent, or trivalent metal ion is bonded to the hygroscopic polymer material.
2. A moisture-absorbing material as claimed in claim 1,
the ligand is a host molecule that forms a clathrate, a chelating agent, or a molecule having a functional group that ionically bonds with the metal ion.
3. A moisture-absorbing material as claimed in claim 2,
the host molecule is at least one molecule selected from the group consisting of cyclodextrin, a crown compound, cyclophene, azacyclophene, calixarene, porphyrin, phthalocyanine, schiff base, and derivatives thereof.
4. A moisture-absorbing material as claimed in claim 2,
the chelating agent is at least one molecule selected from the group consisting of polyalkylene glycol, ethylenediamine, bipyridine, ethylenediamine tetraacetic acid, phenanthroline, and derivatives thereof.
5. A moisture-absorbing material as claimed in claim 2,
the molecule having a functional group is at least one or more molecules selected from the group consisting of carboxylic acid, phosphoric acid, sulfonic acid, and amine.
6. A moisture-absorbing material as claimed in any one of claims 1 to 5,
the hygroscopic polymer material is any one of the following (a) to (e):
(a) a hydrophilic polymer;
(b) a mixture of a stimulus-responsive polymer and a hydrophilic polymer, the polymer having an affinity for water reversibly changed in response to an external stimulus;
(c) a copolymer of a stimulus-responsive polymer and a hydrophilic polymer, the polymer having an affinity for water reversibly changed in response to an external stimulus;
(d) a polymer network in which a stimulus-responsive polymer and a hydrophilic polymer, the affinity of which reversibly changes with water in response to an external stimulus, are mutually impregnated; and
(e) the polymer network is formed by semi-interpenetrating a polymer network with a stimulus-responsive polymer and a hydrophilic polymer, the stimulus-responsive polymer and the hydrophilic polymer having reversibly changed affinity for water in response to an external stimulus.
7. A moisture-absorbing material as claimed in any one of claims 1 to 6,
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 to 80 mol%.
8. A moisture-absorbing material as claimed in any one of claims 1 to 7,
also included are salts of monovalent, divalent, or trivalent metal ions.
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