JP6348382B2 - Heat storage material, heat storage method and heat utilization system using the same - Google Patents

Description

  The present invention relates to the use of a complex compound obtained by coordination of a Schiff base complex and a nitrogen-containing heteroaryl as a heat storage material, a heat storage method using the complex, and a heat utilization system using the heat storage material. .

Conventionally, it has been desired to use surplus heat generated on automobiles and heat energy of sunlight (for example, electromagnetic waves having a longer wavelength than the near infrared). In general, there is a problem that a scene (time) in which heat is generated and a scene that uses (or wants to use) the heat do not always coincide with each other.
For example, when riding a car in winter, there are many benefits if exhaust heat such as heat generated during travel can be used for warming up the engine the next time (for example, the next morning). For example, when the initial warm-up time is shortened, fuel consumption at the start of the engine is reduced, that is, fuel consumption is improved. In addition, the fact that heating can be used almost simultaneously with the ride has the advantage of improving comfort for the passengers.
Taking a house as an example, if the thermal energy of sunlight during the daytime can be used at any time after sunset (for example, the night of the day, the night of the next day, etc.), the utility cost can be reduced. .

As one method for solving the above problems and enjoying these benefits, there is a method of storing energy with a heat storage material using a substance whose three states change with increasing temperature.
As such a heat storage material, there has heretofore been one using sodium pyrophosphate, ionic liquid, glacial acetic acid, erythritol or the like (Patent Documents 1 to 4).
In addition, heat storage materials using metallopolymers or Schiff base complexes have been reported (Patent Documents 5 and 6).
By the way, it has been reported that a certain Schiff base complex forms a coordination bond with pyridine (Non-patent Documents 1 and 2).

Japanese Patent Laid-Open No. 2001-107035 JP 2006-219557 A JP 2005-97530 A Japanese Patent Laid-Open No. 5-32963 JP 2011-74368 A JP 2012-177094

K. Miyokawa et al, Bull.Chem.Soc.Jpn., 55, 104-107 (1982) K. Miyokawa et al, Bull.Chem.Soc.Jpn., 54, 3361-3365 (1981)

  The heat storage materials such as those disclosed in Patent Documents 1 to 4 store heat using latent heat of the material. However, for example, when heat energy is removed, a phenomenon such as a phase change (the three states change) or a dissociated state returns to the base is used, and the energy is stored when the temperature is lowered. When the heat escapes, that is, when the temperature of the heat storage material decreases in a state where the heat is recovered (absorbed), the amount of stored energy also decreases. Therefore, after collecting heat, there is a strong demand for a heat storage material that generates heat with a trigger such as heat without being affected by the external environment such as a temperature drop and a heat utilization system using the same, and uses a metallopolymer or a Schiff base complex. The heat storage material which was there was developed (patent documents 5 and 6).

  The Schiff base complex represented by the formula (I) in Patent Document 6 changes the crystal structure together with heat absorption. This means that the Schiff base complex absorbs heat and changes its crystal structure, thereby reducing energy. Means that In addition, the Schiff base complex can provide a heat storage material that is not affected by changes in the external environment temperature in a state where energy is absorbed and stored (the energy storage amount does not decrease due to a decrease in the external environment temperature). It is known that stored energy can be released by applying a trigger, such as heat or a physical or mechanical stimulus.

  As a result of intensive studies, the present inventors have found that a complex compound obtained by coordinating nitrogen-containing heteroaryl to the Schiff base complex of Patent Document 6 described above is a heat energy such as exhaust heat energy or sunlight. It was found useful for a heat storage material that can be recovered and stored and a heat utilization system using the same, and the present invention was completed.

  The present invention relates to formula (I):

[Where,
R and R ′ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, or an optionally substituted aryl group;
M is a divalent transition metal ion;
A, B, C, D, A ′, B ′, C ′, and D ′ are hydrogen, or two adjacent atoms are bonded to each other, and two carbon atoms to which each is bonded Together form an optionally substituted aryl ring)
The heat storage material characterized by including the complex compound obtained by coordinate-bonding the Schiff base complex shown by these, and nitrogen-containing heteroaryl is provided.
The present invention also provides a heat utilization method using the complex compound.
Furthermore, this invention also provides the heat | fever utilization system provided with said heat storage material.

Since the complex compound of the present invention can recover and store heat energy such as exhaust heat energy, a heat storage material, a heat storage method, and a heat utilization system using the heat storage material can be provided.
Since the Schiff base complex represented by the formula (I) which is coordinated in the complex compound of the present invention can change the crystal structure together with heat absorption, the complex compound of the present invention has the Schiff base system. The complex can store energy by absorbing heat and changing its crystal structure. The complex compound of the present invention storing this energy can release the stored energy by being given an external trigger such as heat or physical / mechanical stimulation.
In addition, since the coordination bond formed between the Schiff base complex represented by the formula (I) in the complex compound of the present invention and the nitrogen-containing heteroaryl dissociates with heat absorption, the complex compound of the present invention is The energy can also be stored when the coordination bond absorbs heat and dissociates. In the complex compound of the present invention storing this energy, the coordination bond is dissociated and the Schiff base complex and the nitrogen-containing heteroaryl are each dissociated, but both compounds are coordinated again. By doing so, the stored energy can be released.
Thus, the complex compound of the present invention can exhibit an excellent heat storage effect due to the change in crystal structure and the dissociation of the compound bond.
Further, the complex compound of the present invention is preferable because it can provide a heat storage material that is not affected by changes in the external environment temperature in a state where energy is absorbed and stored (the amount of stored energy does not decrease due to a decrease in the external environment temperature).

It is a schematic diagram which shows the flow of the air in an engine. It is a schematic diagram of sectional drawing of an air conditioner. It is a schematic diagram which shows the relationship between the flow of air and an air conditioner (especially heater). It is a schematic diagram of Embodiment 1 which collects exhaust heat of an engine from an exhaust manifold. It is a mimetic diagram of Embodiment 2 which collects exhaust heat of an engine from an exhaust pipe. It is a mimetic diagram of Embodiment 3 which collects exhaust heat of an engine from an exhaust pipe, and warms air directly. It is a schematic diagram of Embodiment 4 which collect | recovers the thermal energy of the sunlight in a house. It is a figure which shows the spectral radiation distribution of sunlight. It is a schematic diagram of Embodiment 5 regarding a heat recovery and discharge | release part provided with the thermal storage material of this invention. The result of the thermogravimetric analysis of the complex compound NMTNi-Py2 of this invention is shown. A one-dot chain line indicates a change in DTA (differential heat), and a solid line indicates a change in TGA (weight).

  Hereinafter, the present invention will be described in detail with reference to the drawings depending on cases, but the present invention is not limited thereto.

(Schiff base complex)
Examples of the linear or branched alkyl group having 1 to 18 carbon atoms in R and R ′ of the present invention include, for example, methyl, ethyl, n-propyl, or isopropyl, or linear or branched butyl, pentyl, Examples include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.
As the alkyl group for R and R ′, isopropyl is preferred.

The aryl group in R and R ′ of the present invention may have a ring member of, for example, 5 to 16 members, preferably 6 to 10 members, and the number of rings is, for example, 1 to 4, preferably 1. There may be. Examples of such an aryl group include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring, and a benzene ring and a naphthalene ring are preferable from the viewpoint of the solubility of the ligand. The aryl group in R and R ′ may be optionally substituted, may be unsubstituted, or may be substituted with an alkyl group such as a methyl group or an ethyl group or an aryl group such as a phenyl group. Good.
As the aryl group in R and R ′, a phenyl group that is unsubstituted or substituted with an alkyl group (preferably a methyl group), such as a 2-methylphenyl group, a 3-methylphenyl group, and a 4-methylphenyl group, Substituted phenyl groups and 3-alkyl-phenyl groups, especially 3-methylphenyl groups are preferred.

  In the Schiff base complex represented by the formula (I), R and R ′ may be the same or different from each other, but are preferably the same for ease of synthesis.

In the present invention, any two adjacent ones of A, B, C, D, A ′, B ′, C ′, and D ′ are bonded to each other, together with two carbon atoms to which each is bonded. To form an aryl ring. Such an aryl ring may have, for example, 5 to 16 members, preferably 6 to 10 members, and the number of rings may be, for example, 1 to 4, preferably 1. Good. Examples of such an aryl ring include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring, and a benzene ring and a naphthalene ring are preferable from the viewpoint of the solubility of the ligand. Such an aryl ring may be optionally substituted, unsubstituted, or substituted with an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group. .
In the present invention, A and B are bonded to each other to form an aryl ring, particularly a benzene ring, together with two bonded carbon atoms, and A ′ and B ′ are bonded to each other. Together with two carbon atoms forming an aryl ring, in particular a benzene ring, it is preferred that C, D, C ′ and D ′ are hydrogen.

  R and R ′ are straight-chain or branched alkyl groups having 1 to 18 carbon atoms, particularly octyl groups; A, B, C, D, A ′, B ′, C ′, and D ′ are hydrogen. The Schiff base complex represented by the formula (I) is preferable in that a good heat storage effect can be obtained.

  R and R ′ are straight-chain or branched alkyl groups having 1 to 18 carbon atoms, particularly isopropyl group; A and B are bonded to each other, and together with two carbon atoms to which each is bonded, an aryl ring In particular a benzene ring, A ′ and B ′ are bonded to each other and together with the two carbon atoms to which they are bonded to form an aryl ring, in particular a benzene ring, C, D, C ′, and The Schiff base complex represented by the formula (I) in which D ′ is hydrogen is preferable in that a good heat storage effect can be obtained.

  R and R ′ may be unsubstituted or substituted with an alkyl group such as a methyl group or an ethyl group or an aryl group such as a phenyl group, in particular an aryl group, particularly a phenyl group A and B are bonded to each other to form an aryl ring, particularly a benzene ring, together with two carbon atoms to which they are bonded, and A ′ and B ′ are bonded to each other to bond each other. A Schiff base complex represented by the above formula (I) in which an aryl ring, particularly a benzene ring, together with two carbon atoms forms hydrogen, and C, D, C ′, and D ′ are hydrogen is excellent. It is preferable at the point from which the thermal storage effect is acquired.

  R and R ′ are unsubstituted or a methyl group, particularly a phenyl group which may be substituted at the 3rd and 4th positions, especially the 3rd position, and A and B are bonded to each other to bond each other. Together with two carbon atoms to form an aryl ring, particularly a benzene ring, and A ′ and B ′ are bonded to each other and together with the two carbon atoms to which they are bonded, an aryl ring, particularly a benzene ring The Schiff base complex represented by the formula (I) in which C, D, C ′, and D ′ are hydrogen is preferable in that a good heat storage effect is obtained.

  The divalent transition metal ion (M) of the present invention is not particularly limited as long as it binds (coordinates) to the 2-hydroxyphenyl-1-imine compound that is a ligand. Are selected from periodic transition metal elements, more preferably zinc (II), copper (II), nickel (II), cobalt (II), manganese (II), and iron (II), especially Copper (II) or nickel (II) is preferable, and nickel (II) is particularly preferable.

In the Schiff base complex of the formula (I) of the present invention,
R and R ′ are both octyl groups or phenyl groups that are unsubstituted or substituted with methyl, ethyl, or phenyl groups;
When R and R ′ are both octyl groups, A, B, C, D, A ′, B ′, C ′, and D ′ are hydrogen, or R and R ′ are both unsubstituted or In the case of a phenyl group substituted with a methyl group, an ethyl group, or a phenyl group, A and B are bonded to each other to form a benzene ring together with two carbon atoms to which each is bonded, and A ′ And B ′ are bonded together to form a benzene ring together with two carbon atoms to which each is bonded, and C, D, C ′, and D ′ are hydrogen;
And it is preferable that M is zinc (II), copper (II), nickel (II) or iron (III), particularly copper (II) or nickel (II) from the viewpoint of obtaining a good heat storage effect.

In the Schiff base complex of the formula (I) of the present invention,
R and R ′ are both isopropyl groups, or unsubstituted or methyl groups, in particular the 3- and 4-positions, especially the 3-substituted phenyl group;
A and B are bonded to each other to form a benzene ring together with two bonded carbon atoms, and A ′ and B ′ are bonded to each other together with two bonded carbon atoms. And form a benzene ring, and C, D, C ′, and D ′ are hydrogen;
And, M is zinc (II), copper (II), nickel (II) or iron (III), particularly copper (II) or nickel (II), especially nickel (II), so that a good heat storage effect is obtained. It is preferable at the point obtained.

  Examples of the Schiff base complex represented by the formula (I) include complex compounds shown in the following table.

  The Schiff base complex represented by the formula (I) is preferably NANi, NOTNi, NMTNi, NPTNi, and NIPNi, more preferably NANi and NMTNi, and still more preferably NMTNi.

(Nitrogen-containing heteroaryl)
The nitrogen-containing heteroaryl of the present invention is not particularly limited as long as it has a nitrogen-containing aromatic ring containing, for example, 1 to 3, preferably 1 or 2, and more preferably 1 ring nitrogen atom. The nitrogen-containing aromatic ring may contain, for example, 3 to 14, preferably 5 to 10, more preferably 6 to 10 ring atoms. Although the said nitrogen-containing aromatic ring contains a carbon atom other than a nitrogen atom as a ring atom, you may also contain hetero atoms other than a nitrogen atom, for example, an oxygen atom or a sulfur atom. The nitrogen-containing aromatic ring may be a single ring or a condensed ring, for example, a condensed bicyclic system and a condensed tricyclic system, but is preferably a monocyclic ring.

  As the nitrogen-containing aromatic ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, 1,2,4-triazine ring, 1,2,4,5-tetrazine ring, Pyrrole ring, imidazole ring, pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, 1,3,4-oxadiazole Ring, 1,2,5-oxadiazole ring, 1,3,4-thiadiazole ring, 1,2,5-thiadiazole ring, indole ring, benzimidazole ring, phenanthroline ring, carbazole ring, quinoline ring, isoquinoline ring, Examples thereof include a cinnoline ring, a phthalazine ring, a quinazoline ring, a quinoxaline ring, and a benzodiazine ring.

The nitrogen-containing aromatic ring is unsubstituted or substituted with one or more substituents independently selected from the group of substituents Z. In the present invention, the substituent Z means an amino group, a monoalkylamino group, a dialkylamino group, a monoalkylammonium group, a dialkylammonium group, an alkyl group, an alkoxy group, a halogen group, a —COOH group, a —COONa group, a cyclo An alkyl group, a cycloheteroalkyl group and the like are meant. The nitrogen-containing aromatic ring is preferably unsubstituted or substituted with an amino group, a monoalkylamino group or a dialkylamino group, particularly a dialkylamino group, especially a dimethylamino group.
The number of carbon atoms of the monoalkylamino group, dialkylamino group, monoalkylammonium group, dialkylammonium group, alkyl group, and alkoxy group is not particularly limited, but for example 1 to 18, preferably 1 to 6, More preferably, it is 1-3. The number of carbon atoms of the cycloalkyl group is not particularly limited, but is 3 to 8, preferably 5 to 6. The cycloheteroalkyl group is, for example, a 5 to 16-membered, preferably 6 to 10-membered ring containing at least one heteroatom independently selected from nitrogen, oxygen, and sulfur.

  The nitrogen-containing heteroaryl of the present invention may have one or more of the above nitrogen-containing aromatic rings. When the nitrogen-containing heteroaryl of the present invention has two or more of the above-mentioned nitrogen-containing aromatic rings, these nitrogen-containing aromatic rings may be connected to each other by an appropriate linking group, for example, a linking group L. . In the present invention, the linking group L means a single bond, an alkylene chain (for example, an alkylene chain having 1 to 6 carbon atoms), and preferably a single bond. The nitrogen-containing heteroaryl of the present invention preferably has 1 to 3, more preferably 1 or 2, particularly preferably 1 nitrogen-containing aromatic ring.

  The nitrogen-containing heteroaryl of the present invention is coordinated to the Schiff base complex represented by the above formula (I). In this case, the ring nitrogen atom in the nitrogen-containing heteroaryl is divalent transition of the Schiff base complex. It can coordinate with the metal ion (M). The nitrogen-containing heteroaryl of the present invention may be monofunctional containing one ring nitrogen atom capable of coordinating, or bifunctional containing two, and is preferably monofunctional.

For example, the nitrogen-containing heteroaryl of the present invention has the following formula (III):

(In the above formula, Q is independently of each other a nitrogen-containing aromatic ring as defined above; Z is independently of each other a group as defined above; and m is independently of each other. An integer greater than or equal to 0, for example an integer of 0-6, preferably an integer of 0-3, more preferably 0 or 1; L is, independently of one another, a group as defined above; Independently of each other, an integer of 0 or more, preferably 0, 1, or 2, more preferably 0; p is an integer of 0 or more, such as an integer of 0-6, preferably an integer of 0-3, It is preferably 0 or 1.

For example, the nitrogen-containing heteroaryl of the present invention has the following formula (IV):

(In the above formula, Y is independently a nitrogen atom or a carbon atom; m is independently an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1. Yes; p is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1; Z, L, and l are as defined in Formula (III) above) Can be done.

  In the formulas (III) and (IV), it is preferable that p is 0, p is 1, and 1 is 0 or 1, particularly 0.

The nitrogen-containing heteroaryl of the present invention includes, for example, the following groups:

Selected from the group consisting of:

Selected from the group consisting of

Selected from the group consisting of

(Complex compound)
The complex compound of the present invention can be obtained by coordinating one or more molecules, for example, one molecule or two molecules of the nitrogen-containing heteroaryl per molecule of the Schiff base complex of the formula (I). For example, when M is copper (II), one nitrogen-containing heteroaryl molecule can be coordinated with one molecule of a Schiff base complex, regardless of the type of nitrogen-containing heteroaryl. In addition, when M is nickel (II), one functional (having one ring nitrogen atom) nitrogen-containing heteroaryl (for example, pyridine, 4-dimethylaminopyridine, etc.) per molecule of Schiff base complex Two molecules are bifunctional (having two ring nitrogen atoms) and a nitrogen-containing heteroaryl (for example, 4,4′-bipyridyl, pyrazine, etc.) can be coordinated by one molecule.
The manufacturing method of the complex compound of this invention is not restrict | limited in particular, The method of a nonpatent literature 1 and 2 is illustrated. For example, the complex compound of the present invention can be easily produced according to the process shown in the following scheme 2.

(Where R, R ′, A, B, C, D, A ′, B ′, C ′, and D ′ are as defined in Formula (I) above; X is each independently And represents nitrogen-containing heteroaryl as defined above; n is an integer of 1 or more, preferably 1 or 2)

In step 1 of Scheme 1 above, the Schiff base complex represented by the above formula (I) is converted to
(Method 1) When dissolved in a liquid nitrogen-containing heteroaryl (X) and adding an alcohol such as methanol or ethanol thereto, a complex is formed and a precipitate is formed. Or (Method 2) together with nitrogen-containing heteroaryl (X), for example, dissolved in an organic solvent such as tetrahydrofuran or chloroform, and after heating and stirring, the solution is evaporated and concentrated. A complex is formed to form a precipitate, which can be recovered by filtration to obtain the complex compound of the present invention represented by the formula (II).
The obtained complex compound may be used as it is for the heat storage material of the present invention as it is, but a purified product such as a crystal precipitated by dissolving it in a solvent such as tetrahydrofuran and adding an appropriate amount of ethanol or the like is used. May be.
The Schiff base complex represented by the formula (I) of the starting material is commercially available or can be produced by the method described in Patent Document 6. The starting material X is also commercially available or can be prepared by known methods.

The complex compound of the present invention represented by the formula (II) obtained in the above-mentioned scheme 1 is formed by coordination of X to the divalent transition metal ion (M). Therefore, the following structural formula (V):

Wherein R, R ′, A, B, C, D, A ′, B ′, C ′, and D ′ are as defined in Formula (I) above; Each independently represents a nitrogen-containing heteroaryl as defined above; n is an integer greater than or equal to 1, preferably 1 or 2.

Therefore, when n is 1, this complex compound is, for example,

When n is 2, for example,

Where R, R ′, A, B, C, D, A ′, B ′, C ′, and D ′ are as defined in Formula (I) above. Each X independently represents a nitrogen-containing heteroaryl as defined above).

The complex compound of the present invention was obtained by coordinating the Schiff base complex represented by the formula (I) and nitrogen-containing heteroaryl listed in Table 2 below in 1: 1 or 1: 2. Complex compounds are exemplified. In Table 2, the abbreviations of the Schiff base complexes indicate the compounds shown in Table 1, the abbreviations for the nitrogen-containing heteroaryl indicate the following compounds, and the coordination number per molecule of the Schiff base complexes. The number of molecules of the nitrogen-containing heteroaryl coordinated is shown.

  As a complex compound of the present invention, the complex compound NMTNi-Py2, NANi-DMAP2, NOTNi-DMAP2, NPTNi-PZ, NMTNi-DMAP2, NPTNi-Py2, NIPNi-BPY, NANi-BPY from the point that a good heat storage effect is obtained. , NMTNi-PZ, and NMTNi-BPY, especially complex compounds NMTNi-Py2, NANi-DMAP2, NOTNi-DMAP2, NPTNi-PZ, NMTNi-DMAP2, NPTNi-Py2, and NIPNi-BPY, especially complex compounds NMTNi-Py2, NANi -DMAP2 and NOTNi-DMAP2 are preferred.

(Heat storage material)
The heat storage material of the present invention may be the complex compound of the present invention itself, or may be composed of two or more complex compounds of the present invention, or as long as the effects of the present invention are not impaired. These additives, for example, a binder for increasing the film strength at the time of forming a thin film, and a metal or carbon nanotube (CNT) for increasing the thermal conductivity of the thin film may be contained together with one or more of the above complex compounds. In particular, a heat storage material containing two types of complex compounds is preferable in that the number of heating and cooling cycles until the heat storage phenomenon appears is reduced.
The method for producing the heat storage material of the present invention is not particularly limited. For example, the heat storage material can be produced by stirring and mixing the one or more complex compounds and the additive added as necessary, and uniformly dispersing them. The heat storage material may be used by being filled into a suitable container, for example, a capsule-shaped heat storage material container (heat storage capsule). As a material for the container of such a heat storage capsule, a plastic such as polypropylene or a metal such as aluminum or stainless steel can be used.

(How to use heat)
The present invention also relates to a heat utilization method using the complex compound of the present invention, in particular, a waste heat utilization method. This heat utilization method includes, for example, the following steps:
(Step 1) Crystal structure of the above Schiff base complex by absorbing heat to the complex compound of the present invention obtained by coordination of the Schiff base complex represented by the formula (I) and nitrogen-containing heteroaryl. A step of dissociating the Schiff base complex and the nitrogen-containing heteroaryl;
(Step 2) a step of isolating the Schiff base complex dissociated in Step 1 from the nitrogen-containing heteroaryl;
(Step 3) Step of coordinating the Schiff base complex isolated in Step 2 with the nitrogen-containing heteroaryl to obtain the complex compound and releasing heat; and (Step 4) Dissociation in Step 1 Applying a trigger, such as heat or physical / mechanical, to the Schiff base complex and / or isolated in step 2 and / or the complex compound obtained in step 3 to release heat;
including.

  In the step 2, the nitrogen-containing heteroaryl dissociated in the step 1 may be moved to another place for isolation. In this case, the nitrogen-containing heteroaryl that can be dissociated as a gas can be easily moved to another place by suction or the like, which is advantageous. Examples of such nitrogen-containing heteroaryl include pyridine, 4-dimethylaminopyridine, 4,4'-bipyridyl, and pyrazine.

The present invention provides a heat utilization system using the complex compound of the present invention. Hereinafter, as an embodiment of the heat utilization system of the present invention, a vehicle air conditioning system (Embodiments 1 to 3) and a residential air conditioning system (Embodiment 4). However, the embodiment shown here assumes that heat higher than room temperature is stored. Since the heat storage material of the present invention can also store heat lower than room temperature, that is, there is a use of a cold storage material, the present invention is not limited to these.
Before that, first, the flow of air taken into the engine will be described with reference to FIG. The air taken in from the intake port is supplied to the engine from the intake manifold after dust removal by a filter. The supplied air is combusted with fuel in the engine, and exhaust gas is exhausted from the exhaust manifold together with the combustion heat. The exhaust gas is exhausted with a catalyst and then exhausted from the muffler through the exhaust pipe.
Next, the flow of air in the air conditioner will be described with reference to FIG. The air flow is supplied from the air outlet to the vehicle interior after the air taken in from the inside / outside air switching door is sent out by a blower fan, passes through an evaporator (cooling) and a heater core (heating). The temperature of the blown-out air is controlled by an air mix door located between the evaporator and the heater core. Further, the air to be taken in can be selected from the vehicle interior or the vehicle exterior depending on the position of the inside / outside air switching door. Generally, it is called “inside air mode” when it is taken in from the passenger compartment, and “outside air mode” when it is taken in from outside air.
Next, the flow of air and water in the engine and the air conditioner (particularly the heater) will be described with reference to FIG. The heat utilization system collects heat, particularly waste heat, and reuses it as heat. “Air flow” and “water flow” will be explained in a simple manner from the viewpoint of a heater.
(the flow of air)
The air taken into the engine is discharged as exhaust gas with combustion heat by combustion in the engine. The temperature of the exhaust pipe is the highest in the vicinity of the exhaust manifold, and the temperature decreases as it goes toward the muffler. The temperature of the exhaust pipe is about 500 to 600 ° C. in the exhaust manifold and 200 to 300 ° C. between the catalyst and the muffler in a steady state operation (for example, during constant running at 40 km / h).
(Water flow)
Heat from the engine is removed with cooling water, and when the cooling water reaches a desired temperature (measured with a thermostat), heat is exhausted from the radiator to keep the cooling water constant. Heating with an air conditioner is performed by circulating a part of this cooling water to the heater core.

(Embodiment 1)
A first embodiment in which exhaust heat of the engine is recovered from the exhaust manifold will be described with reference to FIG. The recovered heat is used as a heat source when the cooling water temperature is low, such as when the engine is started.
[Operation] During running, exhaust heat generated in the exhaust manifold is recovered by a heat recovery / release section (shaded area in the figure) provided with the heat storage material of the present invention. The heat storage material can retain the energy of exhaust heat in the substance as a change in crystal structure even after the engine is stopped. When the engine is started again (for example, in the morning of the next day), the energy stored in the heat storage material can be released, and the cooling water (in the third embodiment, air) can be heated.
[Effect] Two effects can be exhibited depending on the place where the recovered heat is supplied. The first is a case where the heater core is mainly heated. When the heater core is heated from the heat recovery / release section using the cooling water loop of the heater core, heating immediately after the engine is started becomes possible. The second case is when cooling water around the engine is heated. Supplying heated cooling water to the engine not only shortens the warm-up operation time when starting the engine, but also provides the benefit of reducing the size (volume) of the catalyst layer downstream of the “air flow” .

(Embodiment 2)
A second embodiment in which exhaust heat of the engine is recovered from the exhaust pipe will be described with reference to FIG. The installation location of the heat recovery / release unit provided with the heat storage material of the present invention is preferably in front of the catalyst having a high exhaust heat temperature (the shaded portion in the figure), but is not particularly limited, and may be any place such as an exhaust manifold. Can be installed. [Operation] and [Effect] are the same as those in the first embodiment.

(Embodiment 3)
A third embodiment in which exhaust heat of the engine is recovered from the exhaust pipe and the air is directly warmed will be described with reference to FIG. Warm-up air is sucked from the “air flow” of the air conditioner by an air pump or the like, heated and then returned to the air conditioner again. The place to return is preferably between the evaporator and the heater core. The place of installation of the heat recovery / release unit provided with the heat storage material of the present invention is preferably a place where the exhaust heat temperature is high, for example, in front of the catalyst (shaded portion in the figure), but is not particularly limited, and any one such as an exhaust manifold It can also be installed. [Operation] is the same as in the first embodiment. [Effect] is that heating is possible immediately after the engine is started.

(Embodiment 4)
Embodiment 4 which collect | recovers the thermal energy of the sunlight in a house is demonstrated using FIG. The wavelength of light used as thermal energy is longer than 780 nm (FIG. 8). Therefore, the form which receives heat energy becomes radiation. A heat recovery / release unit including the heat storage material of the present invention receives sunlight and recovers thermal energy from the sun. Thereafter, the energy stored in the heat storage material is released at any time to heat the cooling water or use the heat for bathing or floor heating. [Effect] is reduction of utility costs.

(Embodiment 5)
Embodiment 5 regarding the heat recovery / release section provided with the heat storage material of the present invention will be described with reference to FIG. The higher the temperature, the better the heat source, but it may be installed at any location such as an exhaust manifold. Any form of conduction, convection, and radiation is possible as the form of energy for transmitting the heat energy from the heat source to the heat storage material.
When using convection, it is preferable to provide a fan or the like for sufficiently stirring the air layer between the heat source and the heat storage material layer. In radiation, it is desirable to install the heat storage material layer so as to be parallel to the radiation surface of the heat source. An air layer is provided in a space between the heat source and the heat storage material layer. This distance is not particularly limited, but may be determined so that the temperature is optimal for the heat storage material. When releasing the energy stored in the heat storage material and transferring it to cooling water or air, the fin material is used to increase the surface area on the discharge side (A surface in the conduction diagram) in order to increase the heat transfer efficiency. It is preferable to install.

The heat recovery / release unit provided with the heat storage material of the present invention is, for example,
A heat recovery part including the heat storage material of the present invention;
Isolation parts 1 and 2 (such as containers) for isolating the Schiff base complex dissociated by heat absorption and the nitrogen-containing heteroaryl separately from the heat recovery part;
Moving devices 1 and 2 (for example, pumps or the like) for individually moving the compounds to the separating parts 1 and 2;
A heat-dissipating part for bringing the compounds into contact with each other to cause a coordinate bond; and a moving device 1 ′ for moving the compounds separately isolated in the isolating parts 1 and 2 to the heat-dissipating part, and 2 '(eg pump)
Is provided.
From the viewpoint of simplifying the apparatus, it is preferable to move only one of the above compounds. That is, in this case, both the isolation part and the moving device can be reduced, and the heat recovery part and the heat release part can be made the same.
For example, while leaving the Schiff base complex dissociated by heat absorption in the heat recovery part, the nitrogen-containing heteroaryl dissociated by heat absorption is moved to the isolation part by a moving device, whereby each of the above compounds is separated. In addition, the nitrogen-containing heteroaryl transferred to the isolation part can be returned to the heat recovery unit again by the transfer device, whereby the above-mentioned compounds can be brought into contact with each other to cause a coordinate bond.

  The following examples illustrate the details of the present invention, but these examples are not intended to limit the present invention.

[Production Example 1]
Production of NPTNi
3.44 g (20.0 mmol) of 2-hydroxy-1-naphthaldehyde was dissolved in 50 ml of ethanol with heating, and 2.14 g (20.0 mmol) of p-toluidine was added. After stirring at 70 ° C. for 1 hour under reflux, completion of the reaction was confirmed by TLC. When the solution was concentrated to about 40 ml with an evaporator, crystals were formed and filtered through a Kiriyama funnel. After drying under reduced pressure at 25 ° C. for 24 hours, yellow crystals (4.70 g, 90%) of 2-hydroxy-1-naphthylmethylidene-4-methylaniline (hereinafter also referred to as “HNPT”) were obtained. 1.06 g (4.00 mmol) of HNPT was dissolved in a mixed solvent of 20 ml of tetrahydrofuran and 30 ml of ethanol, and 50 ml of an ethanol solution of 0.50 g (2.00 mmol) of nickel acetate tetrahydrate was added with stirring. When the mixture was refluxed and stirred at 70 ° C. for 1 hour, crystals were precipitated. The completion of the reaction was confirmed by TLC. The resulting crystals were filtered with a Kiriyama funnel and washed thoroughly with ethanol. Drying under reduced pressure at 25 ° C. for 24 hours gave a crude product of complex compound NPTNi represented by the following formula as greenish brown crystals (1.16 g, 94%). A part of the obtained crystal was dissolved in tetrahydrofuran, and 4-fold volume of ethanol was added to precipitate the crystal. This was filtered and dried under reduced pressure to obtain a purified product of the complex compound NPTNi.

[Production Example 2]
Manufacture of NIPNi
3.44 g (20.0 mmol) of 2-hydroxy-1-naphthaldehyde was dissolved in 50 ml of methanol, and 2.48 g (10.0 mmol) of nickel acetate tetrahydrate and 4.80 g (8.0 mmol) of isopropylamine were added. When the mixture was refluxed and stirred at 60 ° C. for 1 hour, crystals were formed. The mixture was filtered with a Kiriyama funnel and thoroughly washed with methanol. Drying under reduced pressure at 25 ° C. for 24 hours gave a crude product of a complex compound NIPNi represented by the following formula as green crystals (4.71 g, 98%). A part of the obtained crystal was dissolved in tetrahydrofuran, and 4-fold volume of ethanol was added to precipitate the crystal. This was filtered and dried under reduced pressure to obtain a purified product of the complex compound NIPNi.

[Example 1]
Production of Complex Compound NOTNi-DMAP2 A Schiff base complex NOTNi obtained according to the method described in Patent Document 6 and N, N-dimethyl-4-aminopyridine are dissolved in tetrahydrofuran, heated and stirred, and then the solution is evaporated. Upon concentration, a complex is formed and precipitation occurs. It collect | recovered by filtration and the complex compound NOTNi-DMAP2 was obtained.

[Example 2]
Production of Complex Compound NMTNi-Py2 When NMTNi obtained according to the method described in Patent Document 6 is dissolved in pyridine and ethanol is added thereto, a complex is formed and precipitation occurs. The complex compound NMTNi-Py2 was obtained by filtration.

[Example 3]
Production of complex compound NMTNi-DMAP2
A complex compound NMTNi-DMAP2 was obtained based on the method described in Example 1 except that NMTNi obtained according to the method described in Patent Document 6 was used instead of NOTNi.

[Example 4]
Production of complex compound NMTNi-BPY
Example 1 except that NMTNi obtained according to the method described in Patent Document 6 was used instead of NOTNi, and 4,4′-bipyridine was used instead of N, N-dimethyl-4-aminopyridine. The complex compound NMTNi-BPY was obtained based on the method described in 1.

[Example 5]
Production of complex compound NMTNi-PZ
The method described in Example 1 was used except that NMTNi obtained according to the method described in Patent Document 6 was used instead of NOTNi, and pyrazine was used instead of N, N-dimethyl-4-aminopyridine. Based on this, the complex compound NMTNi-PZ was obtained.

[Example 6]
Production of complex compound NANi-DMAP2
A complex compound NANi-DMAP2 was obtained based on the method described in Example 1 except that NANi obtained according to the method described in Patent Document 6 was used instead of NOTNi.

[Example 7]
Production of complex compound NANi-BPY
Example 1 except that NANi obtained according to the method described in Patent Document 6 was used instead of NOTNi, and 4,4′-bipyridine was used instead of N, N-dimethyl-4-aminopyridine. The complex compound NANi-BPY was obtained based on the method described in 1.

[Example 8]
Production of complex compound NPTNi-Py2
The complex compound NPTNi-Py2 was obtained based on the method described in Example 2 using NPTNi produced in Production Example 1 instead of NMTNi.

[Example 9]
Production of complex compound NPTNi-PZ
The complex compound NPTNi- was prepared based on the method described in Example 1, except that NPTNi prepared in Preparation Example 1 was used instead of NOTNi, and pyrazine was used instead of N, N-dimethyl-4-aminopyridine. I got PZ.

[Example 10]
Production of complex compound NIPNi-BPY
Based on the method described in Example 1, except that NIPNi prepared in Preparation Example 2 was used instead of NOTNi and 4,4′-bipyridine was used instead of N, N-dimethyl-4-aminopyridine. As a result, a complex compound NIPNi-BPY was obtained.

[Thermogravimetric analysis]
In the present invention, thermogravimetric analysis was performed with the following apparatus and conditions.
Equipment: DTG-60H manufactured by Shimadzu Corporation
Atmospheric gas: N ₂ (100mL / min)
Container material: Al
Temperature range: RT-500 ℃
Sweep speed: 10 ℃ / min

  The complex compound produced in the above example was dried and then subjected to thermogravimetric analysis. The amount of heat was calculated by comparing the area of the DTA peak of each sample with the area of the DTA peak of indium used as a standard substance. The results of thermogravimetric analysis are shown in Table 3.

  From Table 3, it can be seen that the complex compound of the present invention exhibits endotherm due to the dissociation of the coordination bond between the Schiff base complex and the nitrogen-containing heteroaryl and the change in the crystal structure of the Schiff base complex.

  Moreover, the result of the thermogravimetric analysis of the complex compound NMTNi-Py2 obtained at this time is shown in FIG. FIG. 10 shows that the endotherm (endotherm is 235 kJ / kg) due to the dissociation of the coordination bond between the Schiff base complex NMTNi constituting the complex and pyridine is around 120 ° C., and the crystal structure of the Schiff base complex NMTNi The endotherm (endothermic amount is 74 kJ / kg) due to the change in temperature was observed at around 240 ° C.

[Increase rate of heat storage density]
The endothermic amount of each of the complex compound of the present invention and the liberated Schiff base complex constituting the complex compound was measured according to the above-mentioned thermogravimetric analysis method, and the rate of increase in thermal storage density was determined from the following formula.
Thermal storage density increase rate = [endothermic amount of the complex compound of the present invention] / [caloric amount of Schiff base complex alone]
The results are shown in Table 4.

  From the results of Table 4, it can be seen that the heat storage density of the complex compound of the present invention increases as compared to the complex alone.

  The heat storage material of the present invention can be used in a vehicle exhaust heat utilization system or a house heat utilization system (for example, an air conditioning system).

Claims (11)

Formula (I):

[Where,
R and R ′ are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, or an optionally substituted aryl group;
M is a divalent transition metal ion;
A, B, C, D, A ′, B ′, C ′, and D ′ are hydrogen, or two adjacent atoms are bonded to each other, and two carbon atoms to which each is bonded Together form an optionally substituted aryl ring)
A heat storage material comprising a complex compound obtained by coordination bonding of a Schiff base complex represented by the above formula and a nitrogen-containing heteroaryl having a nitrogen-containing aromatic ring containing a ring nitrogen atom .   The heat storage material according to claim 1, wherein R and R 'are isopropyl, or phenyl which is unsubstituted or substituted with a methyl group.   A and B are bonded to each other to form a benzene ring together with two bonded carbon atoms, and A ′ and B ′ are bonded to each other together with two bonded carbon atoms. The heat storage material according to claim 1, wherein C, D, C ′, and D ′ are hydrogen.   The heat storage material according to any one of claims 1 to 3, wherein the divalent transition metal ion is selected from transition metals in the fourth period of the periodic table.   The heat storage material according to claim 4, wherein the divalent transition metal ion is zinc (II), copper (II), nickel (II), cobalt (II), manganese (II), or iron (II).   The nitrogen-containing heteroaryl has a nitrogen-containing aromatic ring containing 1 to 3 ring nitrogen atoms, wherein the nitrogen-containing aromatic ring contains 3 to 14 ring atoms. The heat storage material according to any one of 5.   The heat storage material according to claim 6, wherein the nitrogen-containing heteroaryl contains 1 to 3 nitrogen-containing aromatic rings. A complex compound was obtained by coordinating one molecule of a Schiff base complex of the formula (I) with one or two nitrogen-containing heteroaryl molecules having a nitrogen-containing aromatic ring containing a ring nitrogen atom , The heat storage material according to any one of claims 1 to 7.   The heat utilization system provided with the heat storage material of any one of Claims 1-8.   The heat utilization system according to claim 9, which is a vehicle waste heat utilization system.   The heat utilization system according to claim 9, which is a residential waste heat utilization system.