JP2005220334A - Heat-utilization material and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide such a heat utilization material belonging to a novel material system that can be utilized in a wide temperature range including a temperature range of 0-150°C. <P>SOLUTION: The heat utilization material comprises a host, which can include a guest to thereby form an inclusion compound, and/or an inclusion compound, which is formed by including the above guest with the above host, with the above host being a salt of a compound and a salt of at least one kind of a compound among its polymers, the compound being expressed by the formula (1): L<SB>m</SB>-A<SB>n</SB>(wherein, L is a basic skeleton such as an unsubstituted or substituted, saturated or unsaturated, linear or branched or cyclic, aliphatic hydrocarbyl group, a 5-memberd or 6-membered cyclic aromatic hydrocarbyl ring, an aromatic heterocyclic single ring, a 2-80 condensed ring group, or the like; (m) is an integer of 1 or more; A is an end group such as cyano group, nitro group, carboxyl group, hydroxy group; (n) is an integer of 1 or more; but the formula (1) contains at least either a hydroxy group or a carboxyl group). Furthermore, a heat reserving material or an adsorbent is formed by this heat utilization material. A thermal storage system contains this heat reserving material. An adsorption heat pump or an air-conditioning system contains this adsorbent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a heat utilization material utilizing the inclusion ability of an organic compound and its application. The heat-utilizing material of the present invention is a heat storage material or adsorbent, etc., for storage and transportation of thermal energy, for example, exhaust heat recovery from various industries and urban environments, storage and transportation of thermal energy, heat exchange in air conditioning equipment, etc. Effectively applied to a wide range of fields.

  Conventionally, heat utilization materials such as latent heat storage materials include ice, sodium sulfate decahydrate, inorganic hydrates such as calcium chloride hexahydrate, organometallic salt hydrates such as sodium acetate trihydrate, paraffin And organic substances such as meso-erythritol have been studied and partially put into practical use. Development of high-density heat transport media by microencapsulating paraffin or emulsifying paraffin has also been performed. Recently, the use of lower alkyl quaternary ammonium salts as heat storage materials and heat transport media has also been reported. In addition, many studies have been made to apply clathrate hydrate with water as a heat storage material.

  On the other hand, an adsorbent using heat of adsorption has also been developed as a heat utilization material, and water-silica gel, water-zeolite, and ethanol-activated carbon are well known as typical combinations. Practical examples include, for example, adsorption heat pumps and humidity control air conditioners. In these devices, the adsorbent that adsorbs water vapor is heated and regenerated, cooled to a temperature that adsorbs water vapor, and adsorbs water vapor again. Let When using heat of 100 ° C. or less obtained by cogeneration systems, fuel cells, automobile engine cooling water, solar heat, geothermal heat, etc., the amount of adsorption changes in a relative water vapor pressure range of 0.05 to 0.3. There is a demand for an adsorbent that is large and has a large adsorption amount (Japanese Patent Laid-Open No. 2003-114067). Conventionally, silica gel, zeolite, activated carbon, and the like are known as water vapor adsorbents, but there is a problem that the amount of adsorption is small and the amount of adsorption is small at the above-described relative water vapor pressure.

  In addition, heat storage and heat increase by chemical reaction have been studied.

Such a heat utilization material (in the narrow sense, a heat storage material, an adsorbent, and a heat transport medium) is required to be used in a temperature range of approximately 0 to 150 ° C. Broadly divided by the temperature range of heat utilization,
(1) 0-15 ° C for air conditioning applications
(2) 15-30 ° C for energy saving and comfortable use in houses
(3) 30-100 ° C for heating air conditioning and exhaust heat recovery applications
(4) 100-150 ° C for exhaust heat recovery applications
There is.

  However, among the heat utilization materials that have been studied so far, only a few are promising, and many have not been put into practical use. For example, heat utilization materials other than ice are sodium sulfate decahydrate (melting point 32.5 ° C) for floor heating applications, paraffin, and sodium acetate trihydrate (melting point 58 ° C) for heating air conditioning applications. Degree.

  The biggest problem with conventional heat-utilizing materials is that the heat-utilizing temperature such as the melting point is inherent to the substance, and it is almost impossible to find new compounds any more. On the other hand, the adsorbent may expand this temperature range by selecting a combination of adsorbent and adsorbate as a working pair, but the range of selection is narrow and the combinations are limited. Therefore, there is little room for development.

For this reason, from the viewpoint of further effective use of thermal energy, the development of more promising heat utilization materials is being demanded mainly in the temperature zones (1) to (4) above. is there.
JP2003-114067

The present invention has been made in view of the above-described conventional situation, and is a heat-utilizing material that can be used in a wide temperature range including a temperature range of 0 to 150 ° C. It is an object to provide a heat utilization material of a completely new material system that is not a limited adsorbent and is not a clathrate hydrate with water as a host.
Another object of the present invention is to provide a high-performance heat storage material made of such a heat utilization material and a heat storage system using the same.
Another object of the present invention is to provide a high-performance adsorbent made of such a heat utilization material, an adsorption heat pump and an air conditioner using the adsorbent.

  The heat utilization material of the present invention includes a host capable of forming a clathrate compound by clathrating a guest, and / or a clathrate compound in which the host clathrates the guest, and the host is represented by the following general formula (I) Or a salt of at least one compound of the multimer or a compound represented by the following general formula (II) and a salt of at least one compound of the multimer: To do.

L _m −A _n (I)
(Wherein L represents a basic skeleton, each independently having a substituent, a saturated or unsaturated linear or branched or cyclic aliphatic hydrocarbon group, a 5- or 6-membered ring Aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or 2-80 condensed ring group, alkylsulfonyl group, alkoxy group, aralkyl group, carbonyl group, alkoxycarbonyl group, acyl group, aryloxy group, dialkylamino A group, a diarylamino group, an amide group, a diaralkylamino group, and these substituents may form a ring with adjacent ones, and may contain S, O, N in the formed ring. M is an integer of 1 or more.
A means a terminal group, and each independently has a halogen atom such as a cyano group, a nitro group, a carboxyl group, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and may have a substituent. 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or 2 to 10 condensed ring group, styryl group, sulfonyl group, alkylsulfonyl group, C1-20 alkyl group, alkenyl group , C1-C20 alkoxy group, cyclic hydrocarbon group, aralkyl group, C1-C20 alkoxycarbonyl group, C2-C20 alkynyl group, acyl group, aryloxy group, dialkylamino group, diarylamino Group, formyl group, amide group, haloalkyl group, diaralkylamino group, and cyclic amino group, and these substituents may be adjacent to each other to form a ring. . n represents an integer of 1 or more. However, general formula (I) contains at least either a hydroxyl group or a carboxyl group. )

（上記一般式（II）において、Ｘ^１，Ｘ^２，Ｘ^３，Ｘ^４，Ｘ^５，Ｘ^６は各々独立にＣ、Ｎ、Ｓ、Ｏ、Ｃ＝Ｏ、Ｓｉのいずれかを表し、ｐ，ｑは各々独立に０以上の整数を示すが、ｐ及びｑの少なくともいずれかは1以上の整数である。なお、一般式（II）で表される６員環はカルボキシル基及び水酸基以外の他の置換基を有していても良く、これらの置換基が互いに結合して該６員環に縮合する、置換基を有していても良い環を形成していても良い。該６員環に縮合する縮合環を有する場合、カルボキシル基及び／又は水酸基はこの縮合環に置換していても良い。）

(In the general formula (II), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ each independently represent any of C, N, S, O, C═O, Si, p , Q each independently represents an integer of 0 or more, but at least one of p and q is an integer of 1 or more, and the 6-membered ring represented by the general formula (II) is a group other than a carboxyl group and a hydroxyl group. Other substituents may be present, and these substituents may be bonded to each other to form a ring which may have a substituent which is condensed to the 6-membered ring. In the case of having a condensed ring fused to the ring, the carboxyl group and / or the hydroxyl group may be substituted with this condensed ring.)

（上記一般式（III）において、ｐ，ｑは各々独立に０以上の整数を示すが、ｐ及びｑの少なくともいずれかは1以上の整数である。なお、一般式（III）で表されるベンゼン環はカルボキシル基及び水酸基以外の他の置換基を有していても良く、これらの置換基が互いに結合して該ベンゼン環に縮合する、置換基を有していても良い環を形成していても良い。該ベンゼン環に縮合する縮合環を有する場合、カルボキシル基及び／又は水酸基はこの縮合環に置換していても良い。） In particular, the host is preferably a salt of at least one compound of the compound represented by the following general formula (III) and its multimer (claim 3).

(In the above general formula (III), p and q each independently represent an integer of 0 or more, but at least one of p and q is an integer of 1 or more. In addition, it is represented by the general formula (III). The benzene ring may have a substituent other than a carboxyl group and a hydroxyl group, and these substituents may be bonded to each other to form a ring having an optionally substituted group. (In the case of having a condensed ring condensed with the benzene ring, the carboxyl group and / or the hydroxyl group may be substituted with this condensed ring.)

Moreover, it is preferable that at least one of X ^{1 to} X ⁶ in the general formula (II) is any one of N, S, O, C═O, and Si.

  That is, as a result of intensive investigations focusing on the inclusion phenomenon as a novel material-based heat-utilizing material that has not been heretofore, the present inventors have found that an inclusion compound can be formed by any combination of a specific organic salt host and guest. Since the formation of the inclusion compound and the dissociation by the release of the guest by the host can occur reversibly, this reversible inclusion phenomenon can be used as a heat utilization material. It has been found that a wide range of heat storage temperatures can be achieved by using it for transfer, including 0 to 150 ° C., in which development is particularly desired and no promising heat utilization material has been provided in the past. A heat utilization material that can be used in a wide temperature range has been developed and the present invention has been achieved.

  Among the inclusion compounds, the host incorporates the guest in stoichiometric ratio. Since the degree of host-guest interaction is broad depending on the host-guest combination and the structure of the inclusion compound, the host-guest bond can be determined by selecting the appropriate host-guest combination according to the purpose. The energy size can be freely selected. In addition, since it has a simple molecular structure, it has excellent characteristics for use in various industrial fields, such as simple production and low cost.

  In the clathrate compound, the host and guest recognize each other and form a molecular complex with non-covalent bonds that are not covalent bonds. Non-covalent bonds are weak bonds, but hydrogen bonds, van der Waals forces, electric charges, dipole moments, ionic bonds, spatial positional relationships, etc. act in a complementary manner, so if integrated, it becomes large energy . When energy larger than the energy forming the clathrate compound is applied, the clathrate complex dissociates into the host and guest, and when the energy is removed, a complex is formed again. That is, the host-guest molecule complex is reversible.

  This balance between reversibility and binding energy is important as a heat utilization material. Therefore, hydrogen bonds often play an important role in providing an inclusion compound as a heat utilization material. The presence of non-covalent bonds in the inclusion compound can be analyzed by analytical methods such as IR and X-ray structural analysis.

  In the present invention, the inclusion compound is used as a heat utilization material for the first time, paying attention to the total of the weak binding action between the host and guest in the inclusion compound and its reversible formation and dissociation. Formation and dissociation of the clathrate compound are reversible, and the dissociated host and guest can be used repeatedly many times, so that they can be used as a heat storage material having a high heat storage amount.

  In particular, when the guest is water, it is preferable because it is inexpensive and there is no concern about environmental pollution.

  In addition, the inclusion compound can be regarded as a phenomenon that the host captures the guest, and the host can also be used as an adsorbent that efficiently adsorbs the guest, and the adsorption heat when the host adsorbs the guest. Alternatively, the latent heat of vaporization of the guest can be used. In this case, for example, it can be preferably used for a desiccant air conditioner, an adsorption heat pump, and the like.

  By the way, the term clathrate compound was generally recognized and used recently, and before that, there was a history that was captured by the concept of solvation, molecular compound, etc. These compounds can also be used as heat utilization materials. In the case of water, the expression hydrate or crystal water may be used.

On the other hand, it is known that when tens of water molecules gather at a low temperature and high pressure to form a cluster, a gas such as methane, ethane, argon, or chlorofluorocarbons is trapped inside the cluster. In addition, a phenomenon in which tetrahydrofuran and a lower quaternary ammonium salt are confined inside the cluster is also known. Some of these phenomena are called clathrate hydrates. The formation of clathrate hydrate is represented by the following formula.
G + xH ₂ O → G · xH ₂ O
(Where G is the guest molecule and x is the number of hydrates)

  This so-called clathrate hydrate is a form in which other molecules are incorporated into the lattice formed by water molecules, so that water molecules may be regarded as a host. However, when dozens of water molecules gather to form a lattice under special conditions, this is a phenomenon that is bound inside the lattice when other molecules exist in the vicinity. It is natural to distinguish from inclusion compounds that form molecular complexes by mutual molecular recognition. In fact, according to the Chemical Handbook (Applied Chemistry II, 5th edition, Nippon Kagaku Kyokai), RIKEN (4th edition, Ryogo Kubo, Saburo Nagakura, Hiroo Iguchi, Hiroshi Ezawa) There is no description in the section of the clathrate compound, and it seems to be preferable to classify them into cluster compounds. In general, the hydration phenomenon and the molecular association phenomenon are not generally called inclusion compounds.

In the present invention, the host is preferably an organic compound having 150 or less carbon atoms.
Moreover, it is preferable that the molecular weight of the host is larger than the molecular weight of the guest included in the host.
The host preferably has a molecular structure having no vacancies (Claim 6).
Moreover, it is preferable that the host includes a guest in a non-covalent bond (Claim 7).

This non-covalent bond preferably includes at least a hydrogen bond. This hydrogen bond is preferably formed through at least one of a hydroxyl group, a carboxyl group, a carbonyl group, a linear or cyclic amino group, an amide group, and an aromatic heterocyclic group that the host or guest has.
The inclusion compound is preferably present as a solid, slurry, or liquid.

  It is preferable that the heat absorption amount of the heat utilization material of the present invention is 20 J / g or more by DSC measurement (claim 8).

In addition, it is preferable that the guest included in the host is water or an organic compound having 100 or less carbon atoms (claim 9).
As this guest, 1 type, or 2 or more types chosen from the group which consists of the organic compound which has a hydroxyl group, the organic compound which has a carbonyl group, the organic compound which has an ether group, and the organic compound containing a hetero atom is mentioned.
Further, the host according to the present invention is preferably a salt of an organic compound having an aromatic hydrocarbon group and / or an aromatic heterocyclic group having a hydroxyl group and / or a carboxyl group (claim 10).

（上記一般式（IV）中、Ｒは、水素、置換基を有していても良い飽和又は不飽和の、直鎖又は環状の脂肪族炭化水素基、置換基を有していても良い芳香族炭化水素基、或いは置換基を有していても良い芳香族複素環基を表し、ｋは１以上の整数を示す。）
この水酸基含有化合物は水、或いは炭素数１〜２０の１価又は多価アルコールであることが好ましい。 With respect to the host, the guest is preferably a hydroxyl group-containing compound represented by the following general formula (IV).

(In the general formula (IV), R is hydrogen, a saturated or unsaturated, linear or cyclic aliphatic hydrocarbon group which may have a substituent, and an aromatic which may have a substituent. Represents an aromatic hydrocarbon group which may have an aromatic hydrocarbon group or a substituent, and k represents an integer of 1 or more.)
This hydroxyl group-containing compound is preferably water or a monovalent or polyhydric alcohol having 1 to 20 carbon atoms.

The heat storage material of the present invention is characterized by comprising such a heat utilization material of the present invention.
The heat storage system of the present invention includes such a heat storage material of the present invention.

The adsorbent of the present invention is made of such a heat utilization material of the present invention, includes at least the host, and adsorbs the adsorbate as a guest.
In the adsorbent of the present invention, the adsorbate is preferably water or a monovalent or polyhydric alcohol having 1 to 20 carbon atoms.

The adsorbent of the present invention is
The adsorption amount of water vapor is 0.1 g / g or more,
In the water vapor adsorption isotherm measured at 25 ° C., the amount of adsorption at a relative water vapor pressure of 0.3 is 0.15 g / g or more.
It is preferable.
The adsorbent of the present invention is
In the water vapor adsorption isotherm measured at 25 ° C., when the relative water vapor pressure is changed by 0.3, it is preferable that the change in the adsorption amount is 0.1 g / g or more.
The adsorbent of the present invention is
The amount of adsorption at a relative water vapor pressure of 0.05 is 0.05 g / g or less.
In the range of relative water vapor pressure 0.05 to 0.30, when the relative water vapor pressure changes 0.20, it has a region where the change in adsorption amount is 0.1 g / g or more,
It is preferable.

The adsorption heat pump of the present invention includes such an adsorbent of the present invention.
The air conditioner of the present invention includes such an adsorbent of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the heat utilization material of the novel material type | system | group excellent in the thermal storage performance which can be used effectively in the wide temperature range including 0-150 degreeC temperature range is provided.
Moreover, according to this invention, the high performance thermal storage material which consists of such a heat utilization material, and the thermal storage system using the same are provided.
Moreover, according to this invention, the high performance adsorbent which consists of such a heat utilization material, the adsorption heat pump using the same, and an air conditioner are provided.

Hereinafter, embodiments of the heat utilization material of the present invention will be described in detail.
First, the clathrate compound according to the present invention will be described.

  An inclusion compound is a heterogeneous complex at the atomic or molecular level generated by a non-covalent bond, and there is a cavity of an appropriate size inside the three-dimensional structure formed by combining atoms or molecules, It is a substance that contains atoms or molecules in a certain composition ratio (Chemical Handbook, Applied Chemistry II, 5th edition, Nippon Kagaku Kyokai). The compound that forms this cavity is the host, and the compound that enters the cavity is the guest. Call. Hosts are roughly classified into organic and inorganic types depending on the constituent elements, and can be further classified into monomolecular systems, polymolecular systems, polymer systems, etc. from the viewpoint of the molecular structure that forms cavities.

In the present invention, a specific organic compound salt is used as a host of such an inclusion compound.
That is, the host according to the present invention is selected from a compound represented by the following general formula (I) or the following general formula (II) and a salt of at least one compound of the multimer.
L _m −A _n (I)

  Here, L means a basic skeleton, each independently having a substituent, a saturated or unsaturated linear or branched or cyclic aliphatic hydrocarbon group, a 5- or 6-membered ring Aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or 2-80 condensed ring group, sulfonyl group, alkylsulfonyl group such as methylsulfonyl group, alkoxy group, aralkyl group, carbonyl group, alkoxycarbonyl group, acyl group , An aryloxy group, a dialkylamino group, a diarylamino group, an amide group, a diaralkylamino group, and preferably having a substituent, a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a pyridyl group, Thienyl group, quinolyl group, phenanthryl group, pyrenyl group, perylenyl group, triazyl group, pyrazyl group, quinoxalyl group, acenaphthyl group Aromatic hydrocarbon ring such as carbazolyl group, indolyl group, furyl group, tolyl group, styryl group or the like, monocyclic group or condensed ring group of aromatic heterocyclic ring; carbon number such as methyl group, ethyl group, tertiary butyl group, etc. Alkyl group having -20; alkoxy group having 1-20 carbon atoms such as methoxy group and ethoxy group; alkoxycarbonyl group having 1-20 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; acetyl group, propionyl group, benzoyl group and the like An aryloxy group such as a phenoxy group and a benzyloxy group; a dialkylamino group such as a diethylamino group and a diisopropylamino group; a diarylamino group such as a diphenylamino group and a phenylnaphthylamino group; an amide group such as an acetylamino group; Diaralkylamines such as dibenzylamino and diphenethylamino groups Groups: alkenyl groups such as vinyl and allyl groups; cyclic hydrocarbon groups such as cyclohexyl, cyclobutyl and cyclopropyl groups; aralkyl groups such as benzyl, phenethyl, phenylpropyl and diphenylmethyl groups; ethynyl groups And alkynyl groups having 2 to 20 carbon atoms such as propynyl group; cyclic amino groups such as morpholino group, thiomorpholino group and piperazino group; and haloalkyl groups such as trifluoromethyl group. These substituents may form a ring with adjacent ones, and may contain S, O, N in the formed ring. In addition, they may form a multimer of dimerization, trimerization or more by directly bonding to each other or other linking group. The linking group is preferably selected from L described above.

  m represents an integer of 1 or more. Preferably m represents an integer of 1 to 20, more preferably an integer of 1 to 15. Unless otherwise specified, the substituent for L is a hydrogen atom.

  A means a terminal group, and each independently has a halogen atom such as a cyano group, a nitro group, a carboxyl group, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and may have a substituent. 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or 2 to 10 condensed ring group, styryl group, sulfonyl group, alkylsulfonyl group such as methylsulfonyl group; methyl group, ethyl group, An alkyl group having 1 to 20 carbon atoms such as a tertiary butyl group; an alkenyl group such as a vinyl group or an allyl group; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group or an ethoxy group; a cyclohexyl group, a cyclobutyl group, a cyclo Cyclic hydrocarbon groups such as propyl group; aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, diphenylmethyl group; methoxycarbonyl group, ethoxycal An alkoxycarbonyl group having 1 to 20 carbon atoms such as an nyl group; an alkynyl group having 2 to 20 carbon atoms such as an ethynyl group and a propynyl group; an acyl group such as an acetyl group, a propionyl group and a benzoyl group; a phenoxy group and a benzyloxy group A dialkylamino group such as a diethylamino group and a diisopropylamino group; a diarylamino group such as a diphenylamino group and a phenylnaphthylamino group; a formyl group; an amide group such as an acetylamino group; a haloalkyl group such as a trifluoromethyl group A diaralkylamino group such as a dibenzylamino group or a diphenethylamino group; a cyclic amino group such as a morpholino group, a thiomorpholino group or a piperazino group, preferably a cyano group, a nitro group, a carboxyl group, a hydroxyl group, or a fluorine atom , Chlorine atom, bromine atom, iodine atom A halogen atom, an amide group, an amino group selected. These substituents may be adjacent to each other to form a ring.

  n represents an integer of 1 or more. Preferably n represents an integer of 1 to 20.

  In addition, when L or A further has a substituent, the substituent is a cyano group, nitro group, carboxyl group, hydroxyl group, sulfonyl group, alkylsulfonyl group, carbonyl group, fluorine atom, chlorine atom, bromine atom. Halogen atoms such as iodine atoms; optionally substituted alkyl groups having 1 to 20 carbon atoms such as methyl groups and ethyl groups; cyclic hydrocarbon groups such as cyclohexyl groups, cyclobutyl groups and cyclopropyl groups An alkenyl group such as a vinyl group which may have a substituent; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group and an ethoxy group which may have a substituent; A good amide group; an alkoxycarbonyl group having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group which may have a substituent; an α-halo which may have a substituent Alkyl group having 2 to 20 carbon atoms such as ethynyl group and propynyl group which may have a substituent; acyl group such as acetyl group, propionyl group and benzoyl group which may have a substituent; Aryloxy groups such as phenoxy group and benzyloxy group which may have substituents; dialkylamino groups such as diethylamino group and diisopropylamino group which may have substituents; Good diarylamino group such as diphenylamino group and phenylnaphthylamino group; Diaralkylamino group such as dibenzylamino group and diphenethylamino group which may have a substituent; Morpholino group, thiomorpholino group and piperazino group And cyclic amino groups such as These substituents may form a ring with adjacent ones, and may contain S, O, N in the formed ring.

  However, general formula (I) contains at least either a hydroxyl group or a carboxyl group. The total number of hydroxyl groups and carboxyl groups in the general formula (I) is preferably 2 or more, and the upper limit is not particularly limited, but is usually 10 or less, preferably 6 or less.

  Although there is no restriction | limiting in particular as a salt of the compound represented by the said general formula (I), and its multimer, Generally, a metal salt is mentioned, About the metal element which forms a metal salt, for example, in the case of an alkali metal , Li, Na, K, Rb, Cs, and Fr. Among them, Li, Na, and K are preferable. In the case of an alkaline earth metal, Be, Mg, Ca, Sr, Ba, and Ra can be mentioned. Among them, Mg, Ca, and Ba are preferable. In the case of transition metals, Cr, Mn, Fe, Co, Ni, Mo, Tc, Ru, Rh, Pd, W, Re, Os, Ir, and Pt can be mentioned, among which Fe, Co, Ni, Pd, and Ir Is preferred. In the case of other metals, Cu, Ag, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb can be mentioned, among which Cu, Ag, Zn, B, Al Ga, In, Si, Ge and Sn are preferable. Of these, Li, Na, K, Mg, Ca, Ba, Fe, Co, Ni, Ir, Cu, Ag, Zn, and Al are particularly preferable. More preferred are Li, Na, K, Mg, Ca, Zn and Al, and particularly preferred are Li, Na, Ca and Mg. These elements have high hydrophilicity, and particularly when water is included, the number of clathrate increases because water also coordinates with the metal. From these things, the heat utilization material of higher calorie | heat amount can be obtained by making it into salt.

  The host according to the present invention is preferably a compound having a salt of an aromatic hydrocarbon compound having a hydroxyl group and / or a carboxyl group and a salt of an aromatic heterocyclic compound having a hydroxyl group and / or a carboxyl group. Here, the number of aromatic hydrocarbon rings or aromatic heterocycles is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 6, and the total number of hydroxyl groups and carboxyl groups is usually 20. Hereinafter, it is preferably 10 or less, particularly 6 or less. In addition, the aromatic hydrocarbon ring and the aromatic heterocyclic ring may have an arbitrary substituent other than the hydroxyl group and the carboxyl group.

  Accordingly, among the compounds represented by the general formula (I), a compound in which an aromatic hydrocarbon group and / or an aromatic heterocyclic group having a hydroxyl group and / or a carboxyl group is contained in L or A is particularly preferable. is there.

Although the preferable example of L in general formula (I) is given to the following, L as a structural component of the organic salt type host which concerns on this invention is not limited to these. Further, in order to select an optimal position in order to obtain desired characteristics, the substitution position of A with respect to L is not particularly limited. For example, L or A may be substituted for A or L by a substituent that L or A has.
In addition, since L of the following illustration does not have a hydroxyl group and a carboxyl group, in this case, A contains at least one of a hydroxyl group and a carboxyl group.

（上記一般式（II）において、Ｘ^１，Ｘ^２，Ｘ^３，Ｘ^４，Ｘ^５，Ｘ^６は各々独立にＣ、Ｎ、Ｓ、Ｏ、Ｃ＝Ｏ、Ｓｉのいずれかを表し、ｐ，ｑは各々独立に０以上の整数を示すが、ｐ及びｑの少なくともいずれかは1以上の整数である。なお、一般式（II）で表される６員環はカルボキシル基及び水酸基以外の他の置換基を有していても良く、これらの置換基が互いに結合して該６員環に縮合する、置換基を有していても良い環を形成していても良い。該６員環に縮合する縮合環を有する場合、カルボキシル基及び／又は水酸基はこの縮合環に置換していても良い。なお、多量体である場合、一般式（II）の化合物は、互いに直接結合ないしは他の連結基によって、２量化、３量化以上の多量体を形成する。） The organic salt host of the present invention which is a salt of at least one compound of the compound represented by the general formula (I) and a multimer thereof is also a compound represented by the following general formula (II) and a multimer thereof. The salt of at least one compound is preferably used.

(In the general formula (II), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ each independently represent any of C, N, S, O, C═O, Si, p , Q each independently represents an integer of 0 or more, but at least one of p and q is an integer of 1 or more, and the 6-membered ring represented by the general formula (II) is a group other than a carboxyl group and a hydroxyl group. Other substituents may be present, and these substituents may be bonded to each other to form a ring which may have a substituent which is condensed to the 6-membered ring. In the case of having a condensed ring fused to the ring, the carboxyl group and / or the hydroxyl group may be substituted on this condensed ring, and in the case of a multimer, the compound of the general formula (II) may be directly bonded to each other or The dimerization, trimerization or higher multimer is formed by the linking group.)

（上記一般式（III）において、ｐ，ｑは各々独立に０以上の整数を示すが、ｐ及びｑの少なくともいずれかは1以上の整数である。なお、一般式（III）で表されるベンゼン環はカルボキシル基及び水酸基以外の他の置換基を有していても良く、これらの置換基が互いに結合して該ベンゼン環に縮合する、置換基を有していても良い環を形成していても良い。該ベンゼン環に縮合する縮合環を有する場合、カルボキシル基及び／又は水酸基はこの縮合環に置換していても良い。なお、多量体である場合、一般式（III）の化合物は、互いに直接結合ないしは他の連結基によって、２量化、３量化以上の多量体を形成する。） Examples of the salt of the compound represented by the general formula (II) and at least one compound of the multimer thereof include, for example, the following general formula (III) in which X ^{1 to} X ⁶ are all carbon atoms in the general formula (II). And a salt of at least one compound of the multimer thereof, and such a compound is particularly suitable for use as an adsorbent.

(In the above general formula (III), p and q each independently represent an integer of 0 or more, but at least one of p and q is an integer of 1 or more. In addition, it is represented by the general formula (III). The benzene ring may have a substituent other than a carboxyl group and a hydroxyl group, and these substituents may be bonded to each other to form a ring having an optionally substituted group. In the case of having a condensed ring condensed with the benzene ring, a carboxyl group and / or a hydroxyl group may be substituted with this condensed ring, and in the case of a multimer, the compound of the general formula (III) Are directly dimerized or other linking groups to form a multimer of dimerization, trimerization or more.)

  In addition, the metal element which forms the salt of at least 1 sort (s) of the compound represented by general formula (II) and (III) and its multimer is what was illustrated as a salt formation metal element in general formula (I). The same thing is mentioned.

A compound in which at least one of X ^{1 to} X ⁶ in the general formula (II) is any one of N, S, O, C═O, and Si is also preferable as the organic host.

  In the general formula (II), p is preferably an integer of 0 to 10, more preferably 0 to 4, and q is preferably an integer of 0 to 20, more preferably 0 to 6. However, at least one of p and q is an integer of 1 or more.

  Examples of the condensed benzene ring or the like with a 6-membered ring include those having a basic skeleton of a naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, perylene ring, carbazole ring, benzoazole ring and the like.

  In addition, when the 6-membered ring in the general formula (II) (including the benzene ring in the general formula (III)) has a substituent other than a carboxyl group and a hydroxyl group, the other substituents include fluorine, chlorine, bromine Halogen such as iodine, cyano group, nitro group, alkyl group which may have a substituent, alkoxy group which may have a substituent, acetyl group which may have a substituent, substituent An amide group which may have a substituent, an ester group which may have a substituent, an alkenyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a substituent Aryloxy group which may have, amino group which may have substituent, aromatic hydrocarbon group which may have substituent, aromatic heterocycle which may have substituent 1 type or 2 types or more of groups etc. are mentioned . Any number of these substituents can be introduced at any position of the 6-membered ring and / or the condensed ring.

  In addition, examples of the substituent that these substituents may further include halogen such as F, Cl, Br, and I, an alkyl group, an alkoxy group, an aryloxy group, an amino group, which may have a substituent, An aromatic hydrocarbon group, a heterocyclic group, etc. are mentioned.

  When the host according to the present invention is a salt of at least one compound of the compound represented by the general formula (III) and its multimer, it is particularly preferable that p + q is 2 or more, and the upper limit thereof is that of the benzene ring. Considering the case where the substituent forms a ring, it is usually 10 or less, preferably 6 or less.

In addition, when the host according to the present invention is a salt of the general formula (II) in which at least one of X ^{1 to} X ⁶ is N, S, O, C═O, or Si, ^When at least one of ^{1 to} X ⁶ is N, or when X ^{1 to} X ⁶ are any of C and C═O, it is preferable that p + q is 1 or more, particularly 1 to 4.

  As long as the host according to the present invention is a salt of at least one of the compounds represented by the general formulas (I), (II), and (III) and its multimer, Any of high molecular weight hosts may be used, but a multimolecular host is particularly preferable because it is inexpensive and can be designed and synthesized in accordance with the purpose. This type of host forms the basic skeletal structure of the inclusion compound, and the guest can be incorporated into the geometrical space formed by the host, such as a tunnel, a layer, and a network, by noncovalent bonding. Further, since the skeletal structure of the clathrate compound can be formed flexibly with respect to the shape and size of the guest, it is preferable in that a wide variety of guests can be accommodated.

  In the clathrate compound according to the present invention, the organic compound salt of the host preferably has 150 or less carbon atoms. When the organic compound salt has more than 150 carbon atoms, the molecular structure of the host becomes complicated and the degree of molecular freedom increases, which is not preferable for firmly incorporating a guest to form an inclusion compound. Moreover, since it will generally become expensive if the structure becomes complicated, it is not preferable for use in industry. The number of carbon atoms of the host is preferably 1 or more, preferably 4 or more, and the upper limit is preferably 140 or less, more preferably 100 or less, particularly preferably 50 or less, and most preferably 30 or less.

  Therefore, when the host is a multimeric salt of the compounds represented by the general formulas (I) to (III), the total number of carbon atoms is preferably as described above.

  When the guest is an organic compound, it is preferable that the molecular weight of the host is larger than the molecular weight of the guest. When the molecular weight of the host is smaller than the molecular weight of the guest, the guest cannot be accommodated in a cavity that can be formed by the host. Further, since the number of guests in the clathrate compound is reduced, the number of non-covalent bonds between the host and the guest is reduced, and the available thermal energy is reduced, which is not preferable. Although there is no general rule regarding the size of the molecular weight of the guest relative to the molecular weight of the host, as a result of studies by the present inventors, it is preferable that the host has a molecular weight that is at least about 5% larger than the guest.

  Further, if the host has a molecular structure having vacancies, the size of the guest is limited by the size of the vacancies in the host, so that the guest is limited. In addition, since a host having holes is expensive, it is not preferable for use in industry. For this reason, the host preferably has a molecular structure having no vacancies.

  The organic salt host according to the present invention is a salt of at least one compound of the compounds represented by the general formulas (I) to (III) and multimers thereof, and preferably the host non-covalently binds the guest. Any of the host and guest having a hydroxyl group, a carboxyl group, a carbonyl group, a linear or cyclic amino group, an amide group, an aromatic heterocyclic group, or a salt thereof. The host and the guest may form a non-covalent bond, but the host preferably has these groups. In addition, molecules of the organic compound salt which is a host may function as a host by being bonded to each other by a non-covalent bond such as a hydrogen bond.

Specific examples of the compounds represented by the general formula (I) and the general formula (II) constituting the organic salt host of the present invention are shown below, but the host according to the present invention is not limited thereto. Absent. In the following, Me represents a methyl group, and Ph represents a phenyl group. ^Also, especially if there is no description for X 1 to X ⁶ represents a carbon.

[Compound represented by formula (I)]

  Of the above exemplified compounds, (2), (6), (14), (15), and (16) are also compounds represented by the general formula (III).

[Compound represented by formula (III) (q ≠ 0)]

[Compound represented by formula (III) (q = 0)]

[Compound represented by the general formula (II), wherein at least one of X ^{1 to} X ⁶ is other than C]

  The compounds of the general formulas (I) and (II) having a carboxyl group or a hydroxyl group are salt-formed at the carboxyl group or hydroxyl group.

Such an organic salt can be obtained by reacting the exemplified compound with a metal compound that forms a salt.
In this case, examples of the metal compound used for the salt formation reaction include halide salts such as chloride, carbonate, bromide, acetate, sulfate, nitrate, and the like. The counter anion when the element forming the salt is present as a cation includes hydroxide ion, cyanide ion, nitrite ion, sulfite ion, perchlorate ion, perbromate ion, periodate ion , Chlorate ion, chlorite ion, hypochlorite ion, phosphate ion, phosphite ion, hypophosphite ion, borate ion, isocyanate ion, hydrosulfide ion, tetrafluoroborate ion, Hexafluorophosphate ion, hexachloroantimonate ion, carboxylate ion (acetate ion, trifluoroacetate ion, benzoate ion, etc.), sulfonate ion (methanesulfonate ion, trifluoromethanesulfonate ion, etc.), alkoxy ion (methoxy) Ion, t-butoxy ion, etc.). These are used as they are or as an aqueous solution.

  In the case of a compound having a plurality of salt-forming groups such as carboxyl groups, all of these may form a salt, or only a part thereof may form a salt. The number of formed salts can be controlled by adjusting the reaction equivalent of the metal compound to be subjected to the salt forming reaction. Residual hydroxyl groups or carboxyl groups are effective for forming intermolecular hydrogen bonds and the like, and taking into account the interaction with the guest to be included, it is possible to draw a wider range of performance by arbitrarily introducing metal. In that point, it is preferable that only a part of the carboxyl group and the hydroxyl group form a salt.

  On the other hand, the guest according to the present invention includes water or an organic compound alone or as a mixture. When the guest is an organic compound, examples of the guest include the following. The number is preferably about 1 to 20.

(1) Organic compound having a hydroxyl group Methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, ethylhexanol, allyl alcohol, propargyl alcohol, cyclohexanol, phenol, cresol, benzyl alcohol, ethylene glycol, propylene glycol, butane Diol, cyclohexanediol, glycerin, etc.

(2) Organic compounds having a carbonyl group A) Ketones: acetone, dimethyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclopentanone, cyclohexanone, acetophenone, propiophenone , Butyrophenone, acetylacetone, benzylmethylketone, benzophenone, benzoquinone, etc. B) Aldehyde: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde etc. C) Ester: methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate , Phenyl acetate, benzyl acetate, ethyl acrylate, ethyl stearate, ethyl benzoate, γ-butyrolactone, δ-valerolacto Etc. D) Carboxylic acid: acetic acid, propionic acid, acrylic acid, oxalic acid, malonic acid, succinic acid

(3) Organic compounds having an ether group Dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, diphenyl ether, anisole, tetrahydrofuran, tetrahydropyran, dioxane, furan, cyclopentanone ethyl methyl Acetal etc.

(4) Nitrogen-containing compounds dimethylformamide, acetamide, phthalimide, ε-caprolactam, urea, urethane, carbodiimide, methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine, ethylenediamine, triethylamine, piperidine, piperazine, pyrrole, oxazole, pyrazole, Pyridine, indole, quinoline, butaneimine, acetonitrile, acrylonitrile, butyl isocyanide, nitrosobenzene, nitromethane, acetone hydroxylamine, hydrazine, hydrazone, triethylamine oxide, benzenediazonium chloride, azobenzene, methyl isocyanate, etc.

(5) Sulfur-containing compounds Dimethyl sulfoxide, dimethyl sulfone, dimethyl sulfide, methyl thiol, diethyl thione, butanthial, thiophene, etc.

(6) Phosphorus-containing compounds Triphenylphosphine, triphenylphosphine oxide, etc.

  However, there is no particular limitation as long as it is a guest that is trapped by the organic salt host and forms an inclusion compound, ammonia, gaseous inorganic compounds such as hydrogen dioxide, caustic soda, caustic potash, lithium hydroxide, magnesium hydroxide, sodium chloride, Solid inorganic compounds such as metal-containing compounds such as lithium bromide can also be used as guests. Further, a liquid inorganic compound or a gas or solid inorganic compound dissolved in a solvent such as water can be used.

（上記一般式（IV）中、Ｒは、水素、置換基を有していても良い飽和又は不飽和の、直鎖又は環状の脂肪族炭化水素基、置換基を有していても良い芳香族炭化水素基、或いは置換基を有していても良い芳香族複素環基を表し、ｋは１以上の整数を示す。） In particular, when the host is a salt of the compound represented by the general formula (II) in the present invention, the guest is preferably a hydroxyl group-containing compound represented by the following general formula (IV).

(In the general formula (IV), R is hydrogen, a saturated or unsaturated, linear or cyclic aliphatic hydrocarbon group which may have a substituent, and an aromatic which may have a substituent. Represents an aromatic hydrocarbon group which may have an aromatic hydrocarbon group or a substituent, and k represents an integer of 1 or more.)

  In the general formula (IV), R is preferably hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group or other alkyl group having 1 to 20 carbon atoms, or unsaturated group such as allyl group. An aromatic hydrocarbon group such as an aliphatic hydrocarbon group and a phenyl group can be mentioned. k is 1, preferably 1-10. Examples of the substituent that the aliphatic hydrocarbon group, aromatic hydrocarbon group, and aromatic heterocyclic group of R may have include a carboxyl group, a halogen such as fluorine, chlorine, bromine, and iodine, a cyano group, a nitro group, and a substituent. An alkyl group which may have a substituent, an alkoxy group which may have a substituent, an acetyl group which may have a substituent, an amide group which may have a substituent, and a substituent. May have an ester group which may have a substituent, an alkenyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. 1 type (s) or 2 or more types, such as an amino group which may be substituted, an aromatic hydrocarbon group which may have a substituent, and an aromatic heterocyclic group which may have a substituent.

  Preferred examples of the compound represented by the general formula (IV) include one or more of water, a monovalent or polyhydric alcohol having 1 to 20 carbon atoms, and the like. More preferably, water, methanol, ethanol, propanol, ethylene glycol, propylene glycol, etc. are mentioned. This is excellent in terms of non-covalent bond energy between molecules, in terms of cost, and in that no harmful compounds are used as an environmental problem.

  In particular, when the heat utilization material of the present invention is an adsorbent, the host constituting the adsorbent is a salt of the compound represented by the general formula (II), and preferably has p + q ≧ 2, A salt of the compound represented by the general formula (III), preferably having p + q ≧ 2, and the adsorbate as a guest is water or a monovalent or polyhydric alcohol having 1 to 20 carbon atoms. preferable.

  In the present invention, since the clathrate compound is used as a heat-utilizing material, the clathrate compound preparation method and existence form are not limited at all as long as it meets the purpose.

  The inclusion compound is prepared by bringing a host molecule and a guest molecule into contact with each other so as to recognize each other and form a complex. In many cases, the formation mechanism of the clathrate compound has not yet been clarified, but the host and guest can use the formation of non-covalent bonds such as hydrogen bonds and the spatial positional relationship and action of the clathrate compound as the driving force. It is considered that the formation of the clathrate compound results in a thermochemically stable state. Among them, those that include a guest by a non-covalent bond are preferable, and it is particularly preferable that the non-covalent bond includes a hydrogen bond. The group capable of forming a hydrogen bond is not particularly limited, but the hydrogen bond is at least one of a hydroxyl group, a carboxyl group, a carbonyl group, a linear or cyclic amino group, an amide group, and an aromatic heterocyclic group that the host or guest has. It is preferably formed via a group.

  There are a number of known methods for preparing clathrate compounds. For example, there is a method in which an inclusion compound is precipitated by dissolving an organic salt host and guest in a suitable solvent. The clathrate compound can also be prepared by contacting them using an appropriate medium that does not dissolve one or both of the organic salt host and guest. Alternatively, the inclusion compound can also be prepared by directly mixing and contacting only the organic salt host and the guest. In this case, the host and guest may be in a solid, liquid, or gas state. When a solvent, a medium, or the like is used for preparing the clathrate compound, the solvent, the medium, or the like may be in a solid, liquid, or gas state.

  The clathrate compound according to the present invention also includes a clathrate compound formed by contacting an organic compound host not forming a salt with a guest by the above method, and then adding a metal compound for forming a salt. It can also be produced by subjecting the host forming the compound to a salt formation reaction. In this case, examples of the metal compound to be added include halides such as chlorides, carbonates and bromides, acetates, sulfates and nitrates. The counter anion when the element forming the salt is present as a cation includes hydroxide ion, cyanide ion, nitrite ion, sulfite ion, perchlorate ion, perbromate ion, periodate ion , Chlorate ion, chlorite ion, hypochlorite ion, phosphate ion, phosphite ion, hypophosphite ion, borate ion, isocyanate ion, hydrosulfide ion, tetrafluoroborate ion, Hexafluorophosphate ion, hexachloroantimonate ion, carboxylate ion (acetate ion, trifluoroacetate ion, benzoate ion, etc.), sulfonate ion (methanesulfonate ion, trifluoromethanesulfonate ion, etc.), alkoxy ion (methoxy) Ion, t-butoxy ion, etc.). These are used as they are or as an aqueous solution.

  The clathrate compounds thus prepared have been obtained in the solid state because they have been attracting attention in fields such as optical resolution, separation and purification, stable preservation of unstable compounds, and sustained release of antibacterial agents. In most cases. However, the clathrate compound is not limited to be in a solid state, and can be present in a liquid state, or can be prepared as a slurry state in which a solid state and a liquid state exist simultaneously. It is also possible to disperse the clathrate compound in a solid state in a suitable liquid medium to form a slurry. In the present invention, any existing form is applicable as long as it matches the use of the heat utilization material.

  In the clathrate compound according to the present invention, the ratio of the host to the guest varies depending on the combination of the host and the guest used, and is not particularly limited. About 1 to 10 moles. However, some hosts have functional groups capable of many non-covalent bonds, especially for the purpose of capturing many guests.

[Heat storage material]
The heat storage material of the present invention is composed of the heat-utilizing material of the present invention, and is capable of accumulating and releasing heat by forming a clathrate compound between the host and guest and dissociating the host and guest. The heat storage function is used. The heat absorption amount of the heat storage material by DSC measurement is usually 20 J / g or more, preferably 50 J / g or more, more preferably 100 J / g or more, further preferably 150 J / g or more, particularly 200 J / g or more, most preferably. Is higher than 250 J / g, and the higher the better, the upper limit is usually 2000 J / g or less.

[Adsorbent]
The adsorbent of the present invention made of the heat utilization material of the present invention will be described below.

<Adsorbent (host)>
The heat utilization material of the present invention includes a host made of a specific organic compound salt, and adsorbs the adsorbate by inclusion of the adsorbate as a guest. In this case, as described above, the host constituting the adsorbent is preferably a salt of the compound represented by the general formula (II), and p + q ≧ 2, particularly represented by the general formula (III). Preferred is a salt of the compound to be obtained, wherein p + q ≧ 2. This is due to the following reason.

  The adsorbent, that is, the hydroxyl group and carboxyl group of the host compound (however, at least a part of these forms a salt), when adsorbing the adsorbate, intermolecular interaction with the adsorbate, particularly hydrogen bonding It is important for the interaction. Since this intermolecular interaction is a non-covalent interaction, it is preferable for reversible adsorption / desorption.

  If the number of hydroxyl groups or carboxyl groups (however, at least a part of these form a salt) is too small, the interaction energy becomes small, so the adsorbate does not adsorb or easily desorbs even if adsorbed. Therefore, it is not preferable. If the number of hydroxyl groups and carboxyl groups (however, at least some of these form a salt) is too large to contribute to the intramolecular interaction of the adsorbent, it cannot be used effectively for the interaction with the adsorbate, Alternatively, since the interaction with the adsorbate is too strong and the interaction energy becomes high, desorption becomes difficult.

  The number of hydroxyl groups and carboxylic acid groups (however, at least a part of these forms a salt) in the case of an adsorbent made of an inclusion compound having a salt of the compound represented by formula (III) as a host By adjusting the above, it is possible to obtain an adsorbent having high adsorption performance in a desired relative water vapor pressure range.

  As the host of the adsorbent, metal salts such as the exemplified compounds (20), (21), (28), (31), (32), and (33) are particularly preferable.

<Adsorbate>
The adsorbate is not particularly limited, but when used as an adsorbent for an adsorption heat pump or a humidity control air conditioner, the compound represented by the general formula (IV) is preferable as the adsorbate, and the adsorbent of the present invention is the general adsorbent. It is preferably used as an adsorbent for the compound represented by the formula (IV).

  As described above, in the general formula (IV), R is preferably an alkyl group having 1 to 20 carbon atoms such as hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, or allyl group. And an unsaturated hydrocarbon group such as phenyl group and an aromatic hydrocarbon group such as phenyl group. k is 1, preferably 1-10. Examples of the substituent that the aliphatic hydrocarbon group, aromatic hydrocarbon group, and aromatic heterocyclic group of R may have include a carboxyl group, a halogen such as fluorine, chlorine, bromine, and iodine, a cyano group, a nitro group, and a substituent. An alkyl group which may have a substituent, an alkoxy group which may have a substituent, an acetyl group which may have a substituent, an amide group which may have a substituent, and a substituent. May have an ester group which may have a substituent, an alkenyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. 1 type (s) or 2 or more types, such as an amino group which may be substituted, an aromatic hydrocarbon group which may have a substituent, and an aromatic heterocyclic group which may have a substituent.

  The adsorbate according to the present invention is preferably water, a monovalent or polyhydric alcohol having 1 to 20 carbon atoms, and more preferably water, methanol, ethanol, propanol, ethylene glycol, propylene glycol and the like. In particular, when used in an adsorption heat pump and a humidity control air conditioner, water is most preferably used as an adsorbate from the viewpoint of economic efficiency and environmental load as well as large latent heat.

  In addition to the above, a compound that is not preferable to be present in a space where an adsorption heat pump or a humidity control device is used, for example, formaldehyde that causes sick house, can be cited as an adsorbate.

<Heat transfer during adsorption / desorption>
The adsorbent of the present invention can be adsorbed and desorbed reversibly as shown in the following formula.
Adsorption α ・ β ← α + β Exotherm Q _exo
Desorption α ・ β → α + β Fever Q _endo

The process of desorbing the adsorbate β by adding heat Q _endo to the adsorbent α and the adsorbate β in this adsorption state is the heat storage process. Conversely, the desorbed adsorbate β is adsorbed on the adsorbent α, and the difference in energy between the desorbed state and the adsorbed state is released as heat Q _{exo in the} heat release process.
Focusing on obtaining heat absorption, that is, cold heat, the adsorbent α and adsorbate adsorbed in the adsorbed state are the state of adsorption by adding cold heat Q _exo to the adsorbed material α and adsorbate β desorbed. The desorption of heat Q _endo due to the desorption of β can be expressed as a cooling process. Although a specific example is mentioned later, it is not limited to warm heat or cold heat.

Two or more kinds of adsorbates may be adsorbed on the adsorbent α.
Here, it is assumed that the adsorbent and adsorbate α and β in the adsorbed state are solid, the adsorbent α is solid, and the adsorbate β is gas as in the following equation.
α ・ β (solid) ← → α (solid) + β (gas)

  A heat storage system and an adsorption heat pump as described below can be made by using the adsorbent of the present invention in which the adsorbate β desorbed becomes a gas.

<Adsorption performance of adsorbent>
The adsorbent of the present invention preferably has a water vapor adsorption amount of 0.1 g / g or more in practice. The water vapor adsorption amount of 0.1 g / g or more means that the difference between the minimum and maximum water vapor adsorption amount is 0.1 g / g or more in the water vapor adsorption isotherm measured at 25 ° C. The water vapor adsorption amount is preferably as large as possible, preferably 0.12 g / g or more, and more preferably 0.15 g / g or more. The upper limit is usually about 0.3 g / g. Further, in the water vapor adsorption isotherm measured at 25 ° C., when the relative water vapor pressure changes by 0.3, more preferably by 0.2, it has a region where the change in adsorption amount is 0.1 g / g or more. preferable. In this case, by appropriately selecting a combination with a system that uses an adsorbent, the system can be operated in a practically advantageous manner within a desired operating range. Among them, in the water vapor adsorption isotherm measured at 25 ° C., the adsorption amount at a relative water vapor pressure of 0.3 is more preferably 0.15 g / g or more, and in the water vapor adsorption isotherm measured at 25 ° C. The amount of adsorption at a relative water vapor pressure of 0.05 is preferably 0.05 g / g or less. The adsorbent of the present invention that satisfies these conditions can also perform regeneration of adsorbent (desorption of adsorbate) with waste heat of about 30 to 100 ° C. and adsorption at a temperature of about 0 to 70 ° C. Further, in the water vapor adsorption isotherm measured at 25 ° C., when the relative water vapor pressure is changed by 0.20 in the range of the relative water vapor pressure of 0.05 to 0.30, more preferably, by 0.15, In the point that the amount of adsorbent used in the device / system can be reduced and the device can be made compact by having a region where the change in adsorption amount is 0.1 g / g or more, that is, the difference in adsorption amount is large. It is advantageous. Also in this case, the upper limit of the adsorption amount difference is usually about 0.3 g / g.

  The adsorbent of the present invention can be preferably used according to the intended use, use conditions, and apparatus system because the adsorption conditions can be controlled by the temperature, pressure, and concentration when adsorbing the adsorbate.

[Application example of heat utilization material of the present invention]
Specifically, the heat utilization material of the present invention is utilized as a heat storage material or an adsorbent. There is no restriction | limiting in particular in the form which adds heat to the heat utilization material of this invention, or takes out heat from a heat utilization material.

The heat utilization material of the present invention is used in various known devices such as a heat storage device to which a heat storage material is applied, an adsorption heat pump to which an adsorbent is applied, an air conditioner to which the adsorbent is applied, and a humidity control device (dehumidification device). The structure of the apparatus to which the heat utilization material of the present invention is applied is not particularly limited.
Examples of application forms of the heat utilization material of the present invention will be described below, but the present invention is not limited to these.

[Heat storage system]
The heat storage system may be any system that uses the heat storage material of the present invention and can store and release heat by forming a clathrate compound between the host and guest and dissociating the host and guest. .

<Example 1>
FIG. 1 is an explanatory view of a capsule-type heat storage system, where (a) is a perspective view of the capsule, (b) is a cross-sectional view of the capsule, and (c) is a flow diagram of the system.

  The capsule 1 has a hollow shell shape made of a material such as a synthetic resin or metal, and has an opening 1a for filling a content 2 made of an inclusion compound or containing an inclusion compound. The opening 1a is sealed with a plug 1b. In FIG. 1, the capsule 1 has a spherical shape, but may have various shapes such as an elliptical shape, a cylindrical shape, an elliptical column shape, a rectangular column shape, a rectangular parallelepiped shape, a cubic shape, a polyhedron shape, a brush shape, a dumbbell shape, and a combination thereof.

  Two or more openings 1a may be provided. The plug 1b may be fixed so as not to be detachable or may be detachable.

  The thickness of the shell portion of the capsule 1 is preferably thin as long as sufficient strength can be secured. In the case of a synthetic resin capsule, the thickness is preferably about 0.2 to 5 mm, particularly about 0.5 to 3 mm.

  As shown in FIG. 1C, the capsule 1 is accommodated in the heat storage tank 4, and the heat source fluid from the heat source device 3 is circulated around the capsule 1. The heat stored in the clathrate compound in the capsule 1 can be supplied to the heat load 6 via the heat exchanger 5.

<Example 2>
FIG. 2 is a schematic cross-sectional view of an ice-on-coil heat storage system. A heat transfer tube 11 is disposed in the heat storage tank 10. The heat transfer tube 11 is in contact with the inclusion compound 12 contained in the heat storage tank 10 or the containing 12 containing the inclusion compound.

  At the time of heat storage, the stored matter 12 is cooled or heated to a temperature equal to or lower than (or higher than) the dissociation point of the clathrate compound by using a refrigerator or a heat pump to store heat. At the time of heat dissipation, by performing the reverse operation to that at the time of heat storage, the clathrate compound is dissociated or clathrated to use heat.

  If the host is solid and the guest is liquid, it can be used in the same manner as the latent heat storage material without applying pressure.

<Example 3>
FIG. 3 is an explanatory diagram of a heat storage system using an adsorbent. In this heat storage system, the adsorbate β is a gas, and the adsorbate β of the present invention is released without being released out of the system. Adsorption and desorption are performed in a sealed space.

  The adsorbent and adsorbate α and β (solid) in the adsorbed state are desorbed, or the adsorbent container 21 that adsorbs the adsorbent α and adsorbate β, and the adsorbate container 22 that stores the desorbed adsorbate β are opened and closed. It is connected by a pipe 24 through a valve 23. The adsorbent container 21 and the adsorbate container 22 can exchange heat with a heat source or a heat load directly or indirectly by a heat transport medium such as water, ethylene glycol aqueous solution, propylene glycol aqueous solution, silicone oil, or air. . Various conventionally known heat exchangers can be used for the adsorbent container 21 and the adsorbate container 22.

In the heat storage process, the adsorbent and adsorbate α and β (solid) in the adsorbed state obtained by obtaining ΔH _H from the heat source are desorbed into the adsorbent α (solid) and adsorbate β (gas). Based on the partial pressure difference of the material β, it moves through the pipe 24 to the container 22 having a lower pressure. The adsorbate β of gas moved into the vessel 22 a liquid adsorbate β condenses releasing heat of condensation [Delta] H _L. At this time, if the on-off valve 23 is closed, the adsorbent α and the adsorbate β are separated and stored in the container 21 and the container 22, respectively, and the energy due to desorption and adsorption of the adsorbent α and the adsorbate β in the adsorbed state for a long time is obtained. Can be held.

In the heat dissipation process, by opening the opening / closing valve 23, the adsorbate β is led to the container 21 based on the partial pressure difference between the adsorbate β in the container 21 and the container 22, and the adsorption energy ΔH _H is released, and the adsorbent α The adsorbents and adsorbates α and β are adsorbed by the adsorbent.

  The heat source of this system is not particularly limited, and examples include solar heat, geothermal heat, electronic equipment (computer server, telephone exchange), exhaust heat from a fuel cell and an internal combustion engine, and the like. The heat load that can be supplied from this system is not particularly limited, and examples thereof include heating air conditioning, hot water supply, and warming up of an internal combustion engine. The cooling load that can be supplied from this system is not particularly limited, and examples include refrigeration, refrigeration, cooling air conditioning, cooling of electronic equipment, heat source of heat pump, and intake air cooling of internal combustion engine.

  Since the adsorbate β moves based on the partial pressure difference between the adsorbate β in the container 21 and the container 22 in both the heat storage process and the heat release process, the adsorbent of the present invention can also be applied to a heat pump as described later. .

[Air conditioning system]
<Example 4>
FIG. 4 is a configuration diagram of an air-conditioning system using the guest adsorption heat of the host.

  A heat transfer tube 26 is disposed in the heat storage tank 25. The heat transfer tube 26 is in contact with the clathrate compound 27 in the heat storage tank 25. The inclusion compound 27 includes a host and a guest that can be adsorbed and desorbed from the host.

  A vaporized guest storage tank 28 for storing a gaseous guest (vaporized guest) desorbed from the clathrate compound 27 is connected to the heat storage tank 25. The heat transfer tube 26 is connected to a fan coil 29, and a heat transfer medium (fluid) can be circulated between the heat transfer tube 26 and the fan coil 29 by a pump (not shown). The fan coil 29 is installed in a room to be air-conditioned.

  This room is, for example, a place where a computer server is installed or a telephone exchange, and has a heat source. In order to prevent the temperature of the room from exceeding a predetermined temperature T ° C. (for example, 50 ° C.), the inclusion compound 27 having a dissociation temperature t ° C. of the host and guest slightly lower than T ° C. or T ° C. is used. ing. The difference (T−t) between T ° C. and t ° C. is preferably about 0 to 50 ° C., particularly about 3 to 40 ° C.

  When the temperature in the room rises to T ° C. or higher, the pump is activated, and the heat transfer medium (fluid) circulates between the tube 26 and the fan coil 29. The heat in the room is guided to the tube 26 by the heat transfer medium, and the clathrate compound 27 is heated. The guest of the clathrate compound 27 is dissociated from the host by this heat and is vaporized, and the temperature of the heat transfer medium is set to about T ° C. by the heat of vaporization. The T.degree. C. heat transfer medium returns to the fan coil 29, so that the temperature in the room is maintained at about T.degree. The guest vaporized from the host is stored in the vaporized guest storage tank 28. The vaporized guest storage tank 28 is provided with a cooling means or a heat dissipation means using, for example, room temperature air or water as a cold heat source, and the pore guest in the storage tank 28 is condensed into a liquid. When the temperature in the room becomes lower than T ° C. such as at midnight, the condensed guest is returned to the heat storage tank 25 and reacted (adsorbed) with the host to form an inclusion compound. The adsorption heat (reaction heat) generated at this time is released into the room through the fan coil 29. In this way, the temperature in the room is prevented from reaching about T ° C. or higher.

[Adsorption heat pump]
<Example 5>
FIG. 5 is a conceptual diagram of an adsorption heat pump using an adsorbent made of the heat utilization material of the present invention. The heat pump shown in FIG. 5 adsorbs the adsorbate β (guest) that is desorbed and becomes a gas, the adsorbent α (host), and the heat of reaction caused by the adsorption / desorption of the adsorbent α and adsorbate β to the heat medium. Towers 101 and 102, an evaporator 104 for taking out the cold heat obtained by desorption and vaporization of the adsorbate β, and an adsorbent and an adsorbate α in a condensed and adsorbed state of the adsorbate β desorbed into a gas. -It is mainly comprised from the condenser 105 which discharge | releases the warm heat obtained by formation of (beta) (clathrate compound) outside.

  The adsorption towers 101 and 102 filled with the adsorbent B are connected to each other by an adsorbate β pipe 30 which is desorbed and becomes a gas, and the pipe 30 is provided with control valves 31 to 34. An evaporator 104 and a condenser 105 are connected to the pipe 30. The adsorption tower 101 and the adsorption tower 102 are connected in parallel between the evaporator 104 and the condenser 105. A return pipe 103 for returning the adsorbate β condensed in the condenser 105 to the evaporator 104 is provided between the condenser 105 and the evaporator 104. Reference numeral 41 denotes an inlet of cooling water that serves as a cooling output from the evaporator 104, and reference numeral 51 denotes an inlet of cooling water to the condenser 105. Reference numerals 42 and 52 denote outlets of the cold water and the cooling water, respectively. The cold water pipes 41 and 42 are connected to an indoor unit 300 arranged to be able to exchange heat with the indoor space (air-conditioned space) and a pump 301 for circulating cold water.

  A heat medium pipe 110 is connected to the adsorption tower 101, and a heat medium pipe 120 is connected to the adsorption tower 102. The heat medium pipes 110 and 120 are provided with switching valves 115, 116, 215 and 216, respectively. A heat medium serving as a heating source or a cooling source for heating or cooling the adsorbent α in the adsorption towers 101 and 102 flows through the heat medium pipes 110 and 120.

  The hot water is introduced from the inlets 213 and 214 by opening and closing the switching valves 115, 116, 215 and 216, passes through the adsorption towers 101 and 102, and is led out from the outlets 114 and 214. The cooling water is also introduced from the inlets 213 and 214 by opening and closing the switching valves 115, 116, 215 and 216, passes through the adsorption towers 101 and 102, and is led out from the outlets 114 and 214. Although not shown, the heat medium pipes 110 and 120 are connected to an outdoor unit disposed so as to be able to exchange heat with the outside air, a heat source unit that generates hot water, and a pump that circulates the heat medium. Examples of the heat source device include an automobile engine, a cogeneration device such as a gas engine and a gas turbine, and a fuel cell. The temperature required to desorb the adsorbent α and the adsorbate β in the adsorbed state composed of the adsorbent α and the adsorbate β varies depending on the combination of the adsorbent and the adsorbate, but is 30 ° C. or higher, preferably 50 ° C., More preferably, it is 60 degreeC or more.

[Air conditioner]
If the adsorbate is harmless, such as water vapor or carbon dioxide, it may be adsorbed with the adsorbate in the air in an open system to form an adsorbent and an adsorbate that are in an adsorbed state, rather than a closed container as described above. it can. When the adsorbate is water vapor in an open system, the adsorbent of the present invention has not only a temperature control function by heat storage and heat dissipation but also a humidity control function by desorption and adsorption of water vapor. It can be used for air conditioners such as wet equipment.

<Operation of humidity control device>
Hereinafter, the operation of the humidity control apparatus using the adsorbent of the present invention will be described with reference to the rotor-rotating desiccant system shown in FIG. 6, but the present invention is not limited to this. For example, it can also be used in a two-column switching desiccant system in which two adsorbent packed towers are switched to adsorption and dehumidification in a batch system.

  The adsorption rotor 60 constituting the humidity control apparatus has a honeycomb shape and includes the adsorbent of the present invention. The adsorbent of the present invention can be applied to and impregnated into a honeycomb-shaped rotor base material to form an adsorbing rotor 60. The adsorbent of the present invention itself can also constitute a honeycomb-like adsorption rotor 60.

  When humidifying the interior of the room with this humidity control device, when the air to be treated W1 from the outside is introduced into the adsorption rotor, the moisture contained in the air to be treated W1 is adsorbed to the adsorbent of the present invention constituting the suction rotor. Dehumidified. Thereby, dry air W2 can be obtained. If this W2 is guided to the humidity control target space, the humidity control target space is dehumidified.

  Since this adsorption rotor is rotating continuously, the moisture adsorbed portion of the adsorption rotor is exposed to the regeneration air W3 having a low relative humidity, so that the moisture is desorbed and regenerated. Further, when the rotor rotates, the regenerated portion of the adsorption rotor is again exposed to the air to be treated W3 and adsorbs moisture. As described above, in the rotor rotating desiccant system, the adsorption and desorption operations can be continuously performed. Further, the regeneration air W3 is humidified to become W4. If this is guided to the humidity control target space, the humidity control target space can be humidified.

  Like a conventionally known desiccant system, not only humidity control but also temperature control can be performed by a desiccant system using the adsorbent of the present invention. Adsorption heat in the adsorption rotor section, desorption heat, and latent heat of vaporization of water obtained by spraying water on dry air can be used as a heat source and a cold source.

<Operation of humidity control air conditioner>
Next, the operation of the humidity control air conditioner using the adsorbent will be described.

  First, the concept of the humidity control air conditioner will be described with reference to FIG. The humidity control air conditioner shown in FIG. 7 includes an adsorbent capable of adsorbing and desorbing adsorbate, an adsorbing portion 61 that is an adsorbing / desorbing portion including the adsorbent, and a regeneration mechanism 63 for regenerating the adsorbent. The air path for circulating the air 62 to be conditioned by the air or the device for forcibly exhausting the conditioned air is provided. The adsorbing portion 61 may have a shape that allows the adsorbent and air for adjusting the humidity to be in sufficient contact with each other, and a rotor shape having a honeycomb structure or the like is used. The regeneration mechanism 63 may be any heat supply mechanism that can supply heat of about 80 ° C. necessary for regeneration of the adsorbent to the adsorption unit 61 in the case of dehumidification, and heat is generated by electric heating or the like inside the apparatus. A heat source such as a heater and a heating coil is used for generation, a mechanism such as a blower for sufficiently transferring heat to the adsorption unit, and a mechanism such as a pipe for supplying the high-temperature gas when a heat source is obtained from outside the apparatus. The external heat source is not particularly limited like the adsorption heat pump, and examples thereof include cogeneration equipment such as a gas engine and a gas turbine, and a fuel cell. In the case of a humidification application, it may be a route through which high-humidity air for reabsorption is circulated.

  Next, although the humidity control effect | action (operation method) by such a dehumidification air conditioner is demonstrated concretely with reference to FIG. 8, it is not limited to this.

  FIG. 8 shows a conceptual diagram of a desiccant air conditioner as an example of a dehumidifying air conditioner. The desiccant air conditioner includes a processing air path 71, a regeneration air path 72, a desiccant rotor 73 to which an adsorbent is attached, two sensible heat exchangers 74 and 75, a heat supply mechanism 76 from a heating source, and a humidifier. 77 is the main component. The processing air is dehumidified by the desiccant rotor 73 and the temperature is increased by the moisture adsorption heat of the desiccant. Thereafter, the first sensible heat exchanger 74 exchanges heat with the regenerated air and cools it. Then, the humidifier 77 humidifies and supplies the air-conditioned space 78. On the other hand, the regenerative air is taken in from the external space, heat-exchanged with the processing air in the first sensible heat exchanger 74 and raised in temperature, and then passed through the second sensible heat exchanger 75 by the heat supply mechanism 76. Heating is performed to lower the relative humidity, and the desiccant rotor 73 is passed through to desorb and regenerate the moisture of the desiccant rotor 73. The sensible heat of the regenerated air after regeneration is recovered by exchanging heat with the regenerated air before heating by the second sensible heat exchanger 75 and then discharged to the outside 79.

  When used in such a dehumidifying air conditioner, a host (adsorbent) that encloses water vapor is used as a guest (adsorbate). The temperature required for the host to dissociate the guest varies depending on the combination of the host and guest, but is 30 ° C. or higher, preferably 50 ° C., more preferably 60 ° C. or higher.

Hereinafter, the present invention will be described more specifically with reference to examples.
As described above, many methods for preparing clathrate compounds are known. In the following, the compound represented by the above general formula (II) or (III) is placed in a glass container together with a guest and heated. After dissolution, a metal salt for forming a salt is added, and the formed salt of the compound represented by the general formula (II) or (III) becomes a host, which is left at room temperature to precipitate the inclusion compound. The method prepared by this was adopted. In addition, an appropriate solvent may be used for dissolving the host compound and the guest compound, but an excess guest compound can be used as a solvent. Was dissolved by heating. When it was difficult for the inclusion compound to precipitate, the solution was spread on a watch glass and dried. An oil bath was used for heating.

  The performance of the clathrate compound as a heat storage material was evaluated by DSC (differential scanning calorimeter). As a device, DSC220C (Seiko Instruments Co., Ltd.) is used, about 5 mg of a heat storage material sample (clathrate compound) is weighed in an open aluminum pan, and the temperature rises at a rate of 5 ° C / min in the range of 25-200 ° C. It was measured. The temperature at which the endothermic peak appeared was defined as the dissociation temperature, and the endothermic peak area was defined as the amount of stored heat.

Example 1
After 10 g of 3,4,5-trihydroxybenzoic acid (Exemplary Compound (31)) is dissolved in 42 ml of water by heating, 3.19 g of sodium carbonate is added as a salt-forming metal compound and dissolved with the generation of carbon dioxide gas. It was. When this solution was left open and allowed to stand at room temperature, 10.46 g of an inclusion compound of Na salt of Exemplified Compound (31) and water was obtained.
When the clathrate of the obtained exemplary compound (31) containing Na salt and water was analyzed by X-ray crystal structure analysis, the Na salt of the exemplified compound (31) as a host included three molecules of water, It was confirmed that the ratio of compound (31) to Na was 1: 1.
FIG. 9 is a TG (thermogravimetric analysis) -DTA and DSC measurement result of the inclusion compound of Na salt and water of the exemplified compound (31), and this inclusion compound dissociates into a host and a guest at 91.4 ° C. The amount of stored heat (dissociation energy) was 596 J / g.

Example 2
Ca salt of Exemplified Compound (20) is obtained by dissolving 0.2 g of Exemplified Compound (20) in 2 ml of water, adding 0.05 g of calcium hydroxide as a salt-forming metal compound, dissolving it, and leaving it at room temperature open. 0.11 g of a brown prism-shaped inclusion compound of water and water was obtained.
As a result of X-ray structural analysis, it was confirmed that the inclusion compound contained 7 molecules of the Ca salt of the exemplified compound (20) as the host, and the ratio of the exemplified compound (20) to Ca was 2: 1. It was.
For the obtained clathrate compound, the dissociation temperature and the heat storage amount (dissociation energy) were examined in the same manner as in Example 1, and the results are shown in Table 7.

Example 3
Except that magnesium hydroxide was used as the salt-forming metal compound, the same procedure as in Example 2 was carried out to obtain 0.26 g of an inclusion compound containing water as a guest.
As a result of X-ray structural analysis, it was confirmed that the inclusion compound was composed of two Mg salts of the exemplified compound (20) as a host, and the ratio of the exemplified compound (20) and Mg was 2: 1. It was done.
For the obtained clathrate compound, the dissociation temperature and the heat storage amount (dissociation energy) were examined in the same manner as in Example 1, and the results are shown in Table 7.

Example 4
Except having used exemplary compound (31) instead of exemplary compound (20), it carried out similarly to Example 2 and obtained 0.04 g of inclusion compounds which made water the guest.
For the obtained clathrate compound, the dissociation temperature and the heat storage amount (dissociation energy) were examined in the same manner as in Example 1, and the results are shown in Table 7.

Example 5
Except that the exemplified compound (33) was used in place of the exemplified compound (20), the same procedure as in Example 2 was carried out to obtain 0.02 g of an inclusion compound containing water as a guest as a solid.
For the obtained clathrate compound, the dissociation temperature and the heat storage amount (dissociation energy) were examined in the same manner as in Example 1, and the results are shown in Table 7.

Example 6
After 0.2 g of Exemplified Compound (28) is dissolved in 1 ml of water by heating, 0.09 g of magnesium hydroxide is added as a salt-forming metal compound and left open at room temperature to obtain Mg salt of Exemplified Compound (28). As a host, 0.15 g of an inclusion compound containing water as a guest was obtained.
For the obtained clathrate compound, the dissociation temperature and the heat storage amount (dissociation energy) were examined in the same manner as in Example 1, and the results are shown in Table 7.

Example 7
After 0.2 g of Exemplified Compound (32) is dissolved in 1 ml of water by heating, 0.22 g of zinc acetate is added as a salt-forming metal compound, and the Zn salt of Exemplified Compound (32) is used as a host by leaving it open at room temperature. Thus, 0.2 g of an inclusion compound containing water as a guest was obtained.
As a result of X-ray structural analysis, it was confirmed that this inclusion compound contained 8 molecules of the Zn salt of the exemplified compound (32) in water, and the ratio of the exemplified compound (32) to Zn was 2: 1.
For the obtained clathrate compound, the dissociation temperature and the heat storage amount (dissociation energy) were examined in the same manner as in Example 1, and the results are shown in Table 7.

Example 8
0.1 g of Exemplified Compound (21) as a host compound was dissolved in 1 ml of water by heating, and 0.02 g of magnesium hydroxide was added as a salt-forming metal compound and dissolved. This solution was developed on a watch glass and left open at room temperature to obtain 0.14 g of an inclusion compound containing Mg salt of Exemplified Compound (21) as a host and water as a guest as a solid.
For the obtained clathrate compound, the dissociation temperature and the heat storage amount (dissociation energy) were examined in the same manner as in Example 1, and the results are shown in Table 7.

  From Table 7, according to the clathrate compound using the salt of the compound represented by the general formula (II) or (III) as a host, the heat storage amount usable in a wide temperature range including a temperature range of 0 to 150 ° C. It is clear that a high heat utilization material is provided.

Example 9
The water vapor adsorption isotherm at 25 ° C. of the Na salt of the exemplary compound (31) obtained in Example 1 was measured under the following measurement conditions. The results are shown in FIG. From FIG. 10, it can be seen that the Na salt of the exemplified compound (31) hardly adsorbs water vapor when the relative water vapor pressure is 0.40 or less, and adsorbs water vapor rapidly in the range of 0.40 to 0.45. . The amount of water vapor adsorption at a relative water vapor pressure of 0.47 is about 0.20, and it can be seen that the Na salt of the exemplified compound (31) specifically adsorbs a large amount of water vapor in a specific narrow relative water vapor pressure region. .

[Water vapor adsorption isotherm measurement conditions]
About Na salt of exemplary compound (31) obtained in Example 1, the vapor | steam adsorption isotherm was measured on condition of the following using Bell Soap 18 by Nippon Bell Co., Ltd.
Air temperature bath temperature: 50 ° C
Adsorption temperature: 25 ° C
Initial introduction pressure: 3.0 torr
Introduced pressure setting points: 0
Saturated vapor pressure: 23.76 mmHg
Equilibrium time: 500 seconds

  Measurement of the TG of the Na salt of the exemplified compound (31) adsorbed with water vapor confirmed that water was desorbed by heat of about 96 ° C. and the Na salt of the exemplified compound (31) of the adsorbent was regenerated. It was.

Example 10
About the Mg salt of the exemplary compound (20) obtained in Example 3, the water vapor adsorption isotherm was measured in the same manner as in Example 9, and the result is shown in FIG.

  Moreover, when TG of Mg salt of the exemplary compound (20) to which water vapor was adsorbed was measured, it was confirmed that water was desorbed with heat of about 140 ° C. and regenerated.

  According to the heat utilization material of the present invention, it is possible to effectively use a wide range of temperatures including a temperature range of 0 to 150 ° C. Adsorbents are provided, which are useful for various heat storage systems using heat storage materials, various adsorption heat pumps and dehumidification air conditioners using adsorbents.

It is explanatory drawing of a capsule-type heat storage system, (a) A figure is a perspective view of a capsule, (b) A figure is sectional drawing of a capsule, (c) A figure is a flowchart of a system. It is a block diagram of a thermal storage system. It is a block diagram of another heat storage system. It is a block diagram of another heat storage system. It is a conceptual diagram of an adsorption heat pump. It is a block diagram of a rotor rotation type desiccant system. It is a principle diagram of a dehumidification air conditioner. It is a conceptual diagram of a desiccant air conditioner. It is a TG-DTA and DSC measurement result of the inclusion compound of Na salt of exemplary compound (31) and water. It is a water vapor | steam adsorption isotherm at 25 degreeC of Na salt of exemplary compound (31). It is a water vapor | steam adsorption isotherm at 25 degreeC of Mg salt of exemplary compound (20).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Capsule 3 Heat source tank 4, 10, 25 Heat storage tank 5 Heat exchanger 6 Heat load 21 Adsorbent container 22 Adsorbate container 60 Adsorption rotor 61 Adsorption part 62 Air path 63 Regeneration mechanism 71 Process air path 72 Regeneration air path 73 Desiccant rotor 74, 75 Sensible heat exchanger 76 Heat supply mechanism 77 Humidifier 78 Air-conditioned space 79 External 101, 102 Adsorption tower 104 Evaporator 105 Condenser

Claims (16)

A host capable of forming a clathrate compound by inclusion of a guest, and / or a clathrate compound in which the host clathrates a guest, wherein the host is a compound represented by the following general formula (I) and a large amount thereof: A heat-utilizing material, which is a salt of at least one compound of the body.
L _m −A _n (I)
(Wherein L represents a basic skeleton, each independently having a substituent, a saturated or unsaturated linear or branched or cyclic aliphatic hydrocarbon group, a 5- or 6-membered ring Aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or 2-80 condensed ring group, alkylsulfonyl group, alkoxy group, aralkyl group, carbonyl group, alkoxycarbonyl group, acyl group, aryloxy group, dialkylamino Group, a diarylamino group, an amide group, a diaralkylamino group, and these substituents may form a ring with the adjacent ones, and may contain S, O, N in the formed ring. M is an integer of 1 or more.
A means a terminal group, and each independently has a halogen atom such as a cyano group, a nitro group, a carboxyl group, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and may have a substituent. 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or 2 to 10 condensed ring group, styryl group, sulfonyl group, alkylsulfonyl group, C1-20 alkyl group, alkenyl group , C1-C20 alkoxy group, cyclic hydrocarbon group, aralkyl group, C1-C20 alkoxycarbonyl group, C2-C20 alkynyl group, acyl group, aryloxy group, dialkylamino group, diarylamino Group, formyl group, amide group, haloalkyl group, diaralkylamino group, and cyclic amino group, and these substituents may be adjacent to each other to form a ring. . n represents an integer of 1 or more. However, general formula (I) contains at least either a hydroxyl group or a carboxyl group. ) A host capable of forming a clathrate compound by inclusion of a guest, and / or a clathrate compound in which the host clathrates the guest, wherein the host is a compound represented by the following general formula (II) and a large amount thereof: A heat-utilizing material, which is a salt of at least one compound of the body.

(In the general formula (II), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ each independently represent any of C, N, S, O, C═O, Si, p , Q each independently represents an integer of 0 or more, but at least one of p and q is an integer of 1 or more, and the 6-membered ring represented by the general formula (II) is a group other than a carboxyl group and a hydroxyl group. Other substituents may be present, and these substituents may be bonded to each other to form a ring which may have a substituent which is condensed to the 6-membered ring. In the case of having a condensed ring fused to the ring, the carboxyl group and / or the hydroxyl group may be substituted with this condensed ring.) 3. The heat utilization material according to claim 2, wherein the host is a salt of at least one compound of a compound represented by the following general formula (III) and a multimer thereof.

(In the above general formula (III), p and q each independently represent an integer of 0 or more, but at least one of p and q is an integer of 1 or more. In addition, it is represented by the general formula (III). The benzene ring may have a substituent other than a carboxyl group and a hydroxyl group, and these substituents may be bonded to each other to form a ring having an optionally substituted group. (In the case of having a condensed ring condensed with the benzene ring, the carboxyl group and / or the hydroxyl group may be substituted with this condensed ring.)   4. The heat utilization material according to claim 1, wherein the host is an organic compound having 150 or less carbon atoms.   5. The heat utilization material according to claim 1, wherein the molecular weight of the host is larger than the molecular weight of the guest included in the host.   6. The heat utilization material according to claim 1, wherein the host has a molecular structure having no vacancies.   7. The heat utilization material according to claim 1, wherein the host includes a guest in a non-covalent bond.   The heat utilization material according to any one of claims 1 to 7, wherein the heat absorption amount by DSC measurement is 20 J / g or more.   9. The heat utilization material according to claim 1, wherein the guest included in the host is water or an organic compound having 100 or less carbon atoms.   10. The salt according to claim 1, wherein the host is a salt of an organic compound having an aromatic hydrocarbon group and / or an aromatic heterocyclic group having a hydroxyl group and / or a carboxyl group. Heat utilization material.   The heat storage material which consists of a heat utilization material of any one of Claim 1 thru | or 10.   A heat storage system including the heat storage material according to claim 11.   The adsorbent which consists of a heat | fever utilization material of any one of Claim 1 thru | or 10, contains the said host at least, and adsorb | sucks an adsorbate as a guest.   14. The adsorbent according to claim 13, wherein in the water vapor adsorption isotherm measured at 25 [deg.] C., when the relative water vapor pressure changes by 0.3, the adsorption amount changes by 0.1 g / g or more.   An adsorption heat pump comprising the adsorbent according to claim 13 or 14.   An air conditioner including the adsorbent according to claim 13 or 14.

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