JP2011074368A - Heat-storing material and heat utilization system using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-storing material capable of recovering and storing heat energy such as exhaust heat energy and sunlight, and a heat utilization system using the heat-storing material. <P>SOLUTION: The heat-storing material comprises a metallopolymer expressed by formula (I) (wherein Rs are each independently 1-18C straight or blanched alkyl which is non-substituted or substituted with -OH, -C(=O)OH, -O-C(=O)H, -NH2, =NH, -NHC(=O)H, -C(=O)NH2 or an aromatic ring, and/or may have -CH=CH-, -C≡C-, -O-, -C(=O)O-, -O-C(=O)-, -NH-, =N-, -N=, -NHC(=O)- or -C(=O)NH- in the middle of the alkyl chain; and M is a divalent transition metal ion). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a heat storage material containing a novel metallopolymer and a heat utilization system using the same.

The metallopolymer widely refers to a polymer containing a metal atom, and examples thereof include a coordination polymer and a macromolecular metal complex. The role of the metal atom contained in the metallopolymer mainly includes the following three.
(1) Role as coordination bond connecting molecules Metal ions and heteroatoms such as O and N form a kind of covalent bond called coordination bond. If an organic molecule (ligand) is designed to coordinate to a plurality of metal ions, a metallopolymer in which the organic molecules are polymerized by coordination bonds can be produced.
(2) Role as a metal complex that plays a role Metallopolymers are linked by covalent bonding (including coordination bonds) between metal atoms and organic molecules, and the bonding sites have the properties of metal complexes. Many metal complexes have electronic, optical, and photochemical functions, and the properties and functions of the metallopolymer can be adjusted by the combination of the type of metal and the organic molecule.
(3) Role as coordination bond to control higher order structure The feature of coordination bond is that it has a direction specific to the type of metal ion. Due to this feature, heteroatoms in the organic molecule coordinated to the metal ion are regularly arranged, and the conformation of the organic molecule is controlled. For example, even an organic molecule having a flexible structure can be fixed on a plane by coordination with a metal.

  Metallopolymers having π-conjugated molecules as ligands have attracted attention from the viewpoint of electronic and optical functions based on interactions between d-π electron systems. Many metal ions have the property of redox activity that allows electrons to be taken in and out reversibly. Therefore, it is considered that electrons can be exchanged between the metal and the ligand if an organic molecule that serves as a ligand also has a redox activity. By polymerizing organic molecules, the action range of electrons is expanded, and the accumulation state of molecules is changed by conformation control. Therefore, it is considered that the function of the metallopolymer can be adjusted by intermolecular interaction. For example, it may be possible to develop plastics that change dielectric constant, magnetism, color, etc. when a certain voltage is applied.

Conventionally, it is desired to use surplus heat generated on automobiles and heat energy of sunlight (for example, electromagnetic waves having a longer wavelength than near infrared rays). 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).

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

  The conventional heat storage material as described above stores heat using latent heat of the material. However, when the heat energy is removed, phenomena such as phase change (the three states change) and the dissociated state return to the base are confirmed. For example, if the temperature at which energy is stored is lowered, the stored heat escapes, that is, if the temperature of the heat storage material changes while heat is recovered (absorbed), the amount of stored energy also varies. For this reason, after absorbing heat, there has been a strong demand for a heat storage material having characteristics that are not affected or hardly affected by the external environment such as temperature and a heat utilization system using the heat storage material.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a heat storage material capable of recovering and storing heat energy such as exhaust heat energy and sunlight, and a heat utilization system using the heat storage material.

  The present invention relates to formula (1):

[In the formula, each R is independently a linear or branched alkyl group having 1 to 18 carbon atoms, wherein the alkyl group is unsubstituted or represents —OH, —C ( _{= O) OH, -O-C} (= O) H, -NH 2, = NH, -NHC (= O) H, -C (= O) NH 2, or is substituted with an aromatic ring, and / Alternatively, the alkyl group has —CH═CH—, —C≡C—, —O—, —C (═O) O—, —O—C (═O) —, —NH—, in the middle of the alkyl chain. ═N—, —N═, —NHC (═O) —, or —C (═O) NH—; M is a divalent transition metal ion]. Provided are a heat storage material and a heat utilization system including the heat storage material.

Since the metallopolymer of the present invention can recover and store heat energy such as exhaust heat energy, a heat storage material and a heat utilization system using the heat storage material can be provided. Furthermore, the metallopolymer of the present invention has an advantage of high durability against heat due to the properties as a metallopolymer.
The metallopolymers of the present invention exhibit thermochromism. This means that the metallopolymer of the present invention absorbed heat, changed its electronic state, and stored energy.
In addition, since the temperature dependence of the absorption spectrum of the metallopolymer of the present invention depends on the type of R group in the above formula (I), the mechanism of thermochromism can be adjusted by the interaction between polymer chains. . This is considered to adjust the mechanism of thermochromism by the complex bond portion by the R group affecting the interaction between the polymer chains. Thereby, a metallopolymer that changes irreversibly by heat can be obtained. Such a metallopolymer is preferable in that it can provide a heat storage material having characteristics that are not affected or hardly affected by an external environment such as temperature while absorbing and storing energy. In addition, such metallopolymers can release stored energy by applying a trigger from the outside. Here, a heat storage material that is not affected or difficult to be affected by the external environment (especially temperature) has the characteristic of maintaining a supercooled state, which is a metastable energy state, by changing the heating / cooling rate, etc. pointing.

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. It is a spectral absorption spectrum of metallopolymer poly-NiL (Oc) Chl. It is a spectral absorption spectrum of metallopolymer poly-NiL (Trd) Chl. It is a spectral absorption spectrum of metallopolymer poly-NiL (Ocd) Chl. It is a spectral absorption spectrum at each temperature of metallopolymer poly-NiL (Oc) Chl. It is a spectral absorption spectrum at each temperature of metallopolymer poly-NiL (Trd) Chl. It is the spectral absorption spectrum in each temperature of metallopolymer poly-NiL (Ocd) Chl. 2 is a DSC spectrum of metallopolymer poly-NiL (Oc) Chl from 0 ° C. to 200 ° C. FIG. 2 is a DSC spectrum of metallopolymer poly-NiL (Dod) Chl from 0 ° C. to 200 ° C. FIG. 2 is a DSC spectrum of metallopolymer poly-NiL (Trd) Chl from 0 ° C. to 200 ° C. FIG. 2 is a DSC spectrum of metallopolymer poly-NiL (Ocd) Chl at 0 ° C. to 200 ° C. FIG. It is a DSC spectrum from 0 ° C. to 200 ° C. of metallopolymer poly-NiL (Dod) -co-5% -NiL (UndCO ₂ H) Chl. Relationship between heating / cooling rate of metallopolymer poly-NiL (Oc) Chl and change in calorific value. Relationship between heating / cooling rate of metallopolymer poly-NiL (Dod) Chl and change in calorific value. Relationship between heating / cooling rate of metallopolymer poly-NiL (Trd) Chl and calorific value change. Relationship between heating / cooling rate of metallopolymer poly-NiL (Ocd) Chl and change in calorific value. Relationship between heating / cooling rate of metallopolymer poly-NiL (Dod) -co-5% -NiL (UndCO ₂ H) Chl and change in calorific value. It is a spectral absorption spectrum of metallopolymer poly-NiL (Oc) THF. It is a spectral absorption spectrum of metallopolymer poly-NiL (Me) THF. It is a spectral absorption spectrum of metallopolymer poly-NiL (tert-Bu) THF. It is a spectral absorption spectrum of metallopolymer poly-NiL (Bn) THF. It is a spectral absorption spectrum at each temperature of metallopolymer poly-NiL (Oc) THF. It is a spectral absorption spectrum at each temperature of metallopolymer poly-NiL (Me) THF. In addition, * means a spectrum before the temperature change, and ** means a spectrum at 25 ° C. after the temperature change. The same applies to FIG. It is a spectral absorption spectrum at each temperature of metallopolymer poly-NiL (Bn) THF. It is a mass spectrum of metallopolymer poly-NiL (Oc) THF.

  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.

(Metallopolymer)
The linear or branched alkyl group having 1 to 18 carbon atoms in each R of the present invention is, for example, methyl, ethyl, n-propyl, or isopropyl, or linear or branched butyl, pentyl, hexyl, It means heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

The alkyl group in each R of the present invention is unsubstituted or substituted with an aromatic ring or the like. The aromatic ring of the present invention includes aromatic carbocycles and aromatic heterocycles.
The aromatic carbocycle 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. Examples of such an aromatic carbocycle 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 ligand solubility.
The aromatic heterocycle includes, for example, at least one heteroatom selected from nitrogen, oxygen, and sulfur, and the ring members may be, for example, 5 to 16 members, preferably 6 to 10 members. May be, for example, 1 to 2, preferably 1. Examples of such an aromatic heterocycle include a 6-membered monocycle such as a pyridine ring or a quinoline ring, and a pyridine ring is preferred from the viewpoint of the solubility of the ligand.
In addition, the aromatic ring of the present invention is unsubstituted or an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 1 to 18 carbon atoms, and an amide having 1 to 8 carbon atoms. Or a carbamoyl group.

As the group which may be contained in the middle of the alkyl chain among the alkyl groups in each R of the present invention, an —O— group is preferable in view of solubility in a polar solvent.
Moreover, it is preferable that the terminal of the alkyl chain by the alkyl group in each R of this invention is substituted by the -OH group from the point of affinity to a polar solvent.

  In the novel metallopolymer of the present invention, each R may be the same or different from each other, or may be the same and partially different, but is preferably the same.

  The divalent transition metal ion of the present invention is not particularly limited as long as it binds (coordinates) to the 2,6-dihydroxynaphthalene-1,5-diimine compound represented by the formula (II) as a ligand. Is preferably selected from transition metal elements of the fourth period of the periodic table, in particular, zinc (II), copper (II), nickel (II), cobalt (II), manganese (II), And iron (II), especially nickel (II).

  In the novel metallopolymer of the present invention, each R is a linear or branched alkyl group having 1 to 18 carbon atoms, particularly a benzyl group, each substituted with an aromatic ring; and M is zinc (II), Copper (II), nickel (II) or iron (III), particularly nickel (II) is preferred.

  N in the formula (I) of the present invention is not particularly limited, but is usually an integer of 1 to 30, preferably an integer of 3 to 10, more preferably an integer of 5 to 6. n can be measured by a conventional method such as matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS).

  Although the manufacturing method in particular of the metallopolymer of this invention is not restrict | limited, It can manufacture simply according to the process shown by the following schemes.

In step 1 of the above scheme, 2,6-dihydroxynaphthalene-1,5-dialdehyde is converted to an amine compound such as various alkylamines or aromatic amines (R—NH ₂ , where R is the above-described formula (I) And is reacted in an alcohol such as methanol to synthesize 2,6-dihydroxynaphthalene-1,5-diimine compound (II). The starting materials 2,6-dihydroxynaphthalene-1,5-dialdehyde and amine compounds are both commercially available or can be prepared by known methods. For example, 2,6-dihydroxynaphthalene-1,5-dialdehyde is described as “H. Houjou, T. Motoyama, S. Banno, I. Yoshikawa, K. Araki,“ Experimental and theoretical studies on constitutional isomers of 2,6 -Dihydroxynaphthalene carbaldehydes. Effects of resonance-assisted hydrogen bonding on the electronic absorption spectra ", J. Org. Chem. 74 (2009) 520-529".
In step 2, the 2,6-dihydroxynaphthalene-1,5-diimine compound (II) synthesized in step 1 is dissolved in an organic solvent such as tetrahydrofuran, chloroform, or dimethylformamide, preferably chloroform, and then transition metal is dissolved therein. When a compound (MX ₂ ), for example, a solution in which a transition metal salt is dissolved in an alcohol such as methanol is added, and preferably heated and more preferably refluxed, a 2,6-dihydroxynaphthalene-1,5-diimine compound The hydrogen ions and transition metal ions in (II) are exchanged to form a polymer complex and precipitation occurs. The metallopolymer (I) of the present invention is obtained by collection by filtration.
In particular, in step 2, a solution in which 2,6-dihydroxynaphthalene-1,5-diimine compound (II) is dissolved in chloroform and a transition metal compound (MX ₂ ) is dissolved in methanol is added thereto, and heated. Refluxing is preferred in that a metallopolymer (I) having a higher molecular weight and excellent thermal stability can be obtained.

In the present invention, the transition metal compound: MX ₂ is selected from divalent transition metal ions, preferably transition metals in the fourth period of the periodic table, particularly preferably zinc (II), copper (II), nickel ( There is no particular limitation as long as II), cobalt (II), manganese (II), or iron (II) can be supplied to the ligand of formula (II) to form the metallopolymer of formula (I). Examples of the transition metal compound used in the present invention include those generally used in the form of a salt of the transition metal, for example, a low-valent inorganic acid salt, organic acid salt, or complex salt of the transition metal. Such transition metal compounds include acetylacetone zinc (II), acetylacetone copper (II), acetylacetone nickel (II), acetylacetone cobalt (II), acetylacetone manganese (II), zinc chloride (II), and cobalt (II) chloride. , Iron (II) chloride, zinc carbonate (II), cobalt carbonate (II), manganese carbonate (II), cobalt oxide (II), zinc acetate (II), copper acetate (II), nickel acetate (II), acetic acid Examples include cobalt (II), manganese acetate (II), zinc stearate (II), cobalt stearate (II), manganese stearate (II), and zinc lactate (II). Absent. The use of zinc (II) acetate, copper (II) acetate, nickel (II) acetate or iron (II) chloride is preferred.

The properties, optical properties, and thermal responsiveness of the metallopolymer of the present invention are as follows.
(Properties)
The metallopolymer of the present invention exhibits various properties such as red to tan, gel or powder depending on the type of R and the type of M. The metallopolymer of the present invention becomes a solid powder upon drying, and a thin film can be formed by rubbing on a glass plate with a hard material such as the back surface of the case.
(Optical properties)
The metallopolymer of the present invention is a dark reddish brown to tan solid in a dry powder state, but transmits light when formed into a thin film having a thickness of about several microns. The transmitted light is reddish brown to yellowish brown and varies depending on the type of R and the type of M.
(Thermal response)
The metallopolymers of the present invention are stable without decomposition in the temperature range of -180 ° C to 210 ° C. The color tone of the metallopolymer of the present invention formed on a glass substrate changes by heating or cooling. The color tone changes reversibly or irreversibly according to the temperature change, and the relationship between color tone and temperature and the reversibility vary depending on the type of R.

(Heat storage material)
The heat storage material of the present invention may be the metallopolymer itself of the present invention, or other additives, for example, a binder for increasing the film strength during thin film formation, In order to increase the thermal conductivity, a metal, carbon nanotube (CNT) or the like may be included together with the metallopolymer. 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 metallopolymer and the additive added as necessary, and uniformly dispersing it. This heat storage material may be used by being filled into an appropriate 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.

Hereinafter, the vehicle air conditioning system (Embodiments 1 to 3) and the residential air conditioning system (Embodiment 4) will be described as embodiments of the heat utilization system of the present invention. The embodiment shown here is heat higher than room temperature. It is assumed to store heat. 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. In heating with an air conditioner, a part of this cooling water is circulated to the heater core and heat is exchanged to warm up the air.

(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 complex structure (change in bonding form, etc.) 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] The cooling water is heated by the heat stored in the heat storage material, and two effects can be exhibited depending on the place where the heat is supplied. The first is a case where the heater core is mainly heated. The heater core is heated from the heat recovery / release section using a cooling water loop of the heater core. Thereby, heating immediately after the engine is started is possible. The second case is when the engine is heated with heated cooling water. 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. 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 following examples illustrate the details of the present invention, but these examples are not intended to limit the present invention.

[Example 1]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and octylamine (258 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-dioctylimine. Dissolve 2,6-dihydroxynaphthalene-1,5-dioctylimine (44 mg) in 10 mL of chloroform, and add a methanol solution of nickel acetate tetrahydrate prepared separately to the ligand and metal ion moles. The ratio was added to 1: 1 and refluxed for 24 hours. The dark red gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Oc) Chl.

[Example 2]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and dodecylamine (370 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-didodecylimine. Dissolve 2,6-dihydroxynaphthalene-1,5-didodecylimine (275 mg) in 12.5 mL of chloroform, and add 1 mL of a separately prepared methanol solution of nickel acetate tetrahydrate to the ligand and metal. The mixture was added so that the molar ratio of ions was 1: 1 and refluxed for 24 hours. The dark red gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Dod) Chl.

[Example 3]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and tridecylamine (399 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-ditridecylimine. 2,6-dihydroxynaphthalene-1,5-ditridecylimine (58 mg) was dissolved in 10 mL of chloroform, and a separately prepared methanol solution of nickel acetate tetrahydrate was added to the ligand and metal ions. The mixture was added so that the molar ratio was 1: 1, and refluxed for 24 hours. The dark red gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Trd) chl.

[Example 4]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and octadecylamine (539 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-dioctadecylimine. Dissolve 2,6-dihydroxynaphthalene-1,5-dioctadecylimine (72 mg) in 10 mL of chloroform and add a separately prepared methanol solution of nickel acetate tetrahydrate to the ligand and metal ions. The mixture was added so that the molar ratio was 1: 1, and refluxed for 24 hours. The dark red gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Ocd) Chl.

[Example 5]
2,6-dihydroxynaphthalene-1,5-dialdehyde (430 mg) was suspended in 100 mL of ethanol, and ω-aminododecanoic acid (860 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered, washed thoroughly with ethanol and tetrahydrofuran, respectively, and 2,6-dihydroxynaphthalene-1,5-diundecylimine-12,12′-dicarboxylic acid (hereinafter “H ₂ ”). L (UndCO ₂ H) ”was recovered (yellow solid 1.13 g, 93%). H ₂ L (UndCO ₂ H) (2.44 g) and triethylamine (0.81 g) were dissolved in 90 mL of dimethylformamide, and 10 mL of a separately prepared methanol solution of nickel acetate tetrahydrate was added to the ligand. The metal ions were added at a molar ratio of 1: 1 and refluxed for 24 hours. The yellowish brown gel-like precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure at 25 ° C. for 24 hours to obtain a metallopolymer poly-NiL (UndCO ₂ H) DMF (2.19 g, 82%).

[Example 6]
2,6-dihydroxynaphthalene-1,5-didodecylimine (2.18 g) prepared in Example 2 and H ₂ L (UndCO ₂ H) (0.024 g) were suspended in 90 ml of chloroform, 10 mL of a separately prepared methanol solution of nickel acetate tetrahydrate was added so that the molar ratio of ligand to metal ion was 1: 1, and the mixture was refluxed for 24 hours. The reddish brown precipitate generated in the reaction solution was filtered and thoroughly washed with methanol and chloroform, respectively. And dried under vacuum for 24 hours 25 ° C., to obtain metallo polymer poly-NiL (Dod) -co- 1% -NiL the _{(UndCO 2 H) Chl (2.15} g, 88%).

[Example 7]
2,6-dihydroxynaphthalene-1,5-didodecylimine (2.09 g) prepared in Example 2 and H ₂ L (UndCO ₂ H) (0.12 g) were suspended in 90 ml of chloroform, 10 mL of a separately prepared methanol solution of nickel acetate tetrahydrate was added so that the molar ratio of ligand to metal ion was 1: 1, and the mixture was refluxed for 24 hours. The reddish brown precipitate generated in the reaction solution was filtered and thoroughly washed with methanol and chloroform, respectively. And dried under vacuum for 24 hours 25 ° C., to obtain metallo polymer poly-NiL (Dod) -co- 5% -NiL the _{(UndCO 2 H) Chl (2.29} g, 94%).

[Example 8]
An appropriate amount of metallopolymer poly-NiL (Oc) Chl was taken in a case and sprayed onto a glass slide. A thin film was made by rubbing poly-NiL (Oc) Chl on the glass surface on the back of the case. The thin film was observed with an optical microscope, and it was visually confirmed that the color tone of the thin film was dark red, and the transmitted light was introduced into the spectroscope through an optical fiber to record a spectral absorption spectrum. The spectrum is shown in FIG.

[Example 9]
An appropriate amount of metallopolymer poly-NiL (Trd) Chl was taken in a case and spread on a slide glass. A thin film was made by rubbing poly-NiL (Trd) Chl on the glass surface on the back of the case. The thin film was observed with an optical microscope, and it was visually confirmed that the color tone of the thin film was dark red, and the transmitted light was introduced into the spectroscope through an optical fiber to record a spectral absorption spectrum. The spectrum is shown in FIG.

[Example 10]
An appropriate amount of metallopolymer poly-NiL (Ocd) Chl was taken in a case and sprayed onto a glass slide. A thin film was made by rubbing poly-NiL (Ocd) Chl on the glass surface on the back of the case. The thin film was observed with an optical microscope, and it was visually confirmed that the color tone of the thin film was dark red, and the transmitted light was introduced into the spectroscope through an optical fiber to record a spectral absorption spectrum. The spectrum is shown in FIG.

[Example 11]
An appropriate amount of metallopolymer poly-NiL (Oc) Chl was taken in a case and sprayed onto a cover glass of 15 mmφ. A thin film was made by rubbing poly-NiL (Oc) Chl on the glass surface on the back of the case. Set the cover glass on a temperature variable stage, observe the thin film with an optical microscope at 30 ° C, visually confirm that the color tone of the thin film is red-orange, and introduce the transmitted light into the spectroscope with an optical fiber. Absorption spectra were recorded. The stage was brought to 30 ° C., heated to + 300 ° C., and then brought to 30 ° C. again. The spectrum at each temperature is shown in FIG. When heated to 300 ° C., the peak dulled and the absorption edge moved to the longer wavelength side, and a change in color tone was confirmed visually. When cooled to 30 ° C. again, the wavelength remained shifted and the peak was sharper than the initial state.

[Example 12]
An appropriate amount of metallopolymer poly-NiL (Trd) Chl was taken in a case and sprayed onto a 15 mmφ cover glass. A thin film was made by rubbing poly-NiL (Trd) Chl on the glass surface on the back of the case. Set the cover glass on a temperature variable stage, observe the thin film with an optical microscope at 30 ° C, visually confirm that the color of the thin film is reddish orange, and introduce the transmitted light into the spectroscope with an optical fiber. Absorption spectra were recorded. The stage was brought to 30 ° C., heated to + 300 ° C., and then brought to 30 ° C. again. The spectrum at each temperature is shown in FIG. When heated to 300 ° C., the peak dulled and the absorption edge moved to the longer wavelength side, and a change in color tone was confirmed visually. When cooled to 30 ° C. again, the wavelength remained shifted and the peak was sharper than the initial state.

[Example 13]
An appropriate amount of metallopolymer poly-NiL (Ocd) Chl was taken in a case and sprayed onto a cover glass of 15 mmφ. A thin film was made by rubbing poly-NiL (Ocd) Chl on the glass surface on the back of the case. Set the cover glass on a temperature variable stage, observe the thin film with an optical microscope at 25 ° C, visually confirm that the color of the thin film is reddish orange, and introduce the transmitted light into the spectroscope with an optical fiber. Absorption spectra were recorded. The stage was brought to 30 ° C., heated to + 300 ° C., and then brought to 30 ° C. again. The spectrum at each temperature is shown in FIG. When heated to 300 ° C., the peak dulled and the absorption edge moved to the longer wavelength side, and a change in color tone was confirmed visually. When it was cooled again to 30 ° C., the wavelength remained almost unchanged and the peak was sharper than the initial state.

[Example 14]
Differential scanning calorimeter (DSC) measurement (measurement method)
The metallopolymer differential scanning calorimeter was measured using the following apparatus and conditions.
Equipment: Bruker AXS Co., Ltd. DSC3100SA
Sample container: Aluminum open cell Temperature range: 0-200 ° C
Heating / cooling rate: 2-40 ° C / min
Purge gas: N ₂
Cooling method: Liquid N ₂

(Confirmation of endothermic behavior)
Metallopolymers poly-NiL (Oc) Chl, poly-NiL (Dod) Chl, poly-NiL (Trd) Chl, poly-NiL (Ocd) Chl, and poly-NiL (Dod) -co-5% -NiL (UndCO _{For 2} H) Chl, its endothermic behavior was measured as follows, and the results are shown in FIGS. 16 to 20 (2 cycles).
About 5 to 8 mg of the metallopolymer after drying was weighed into an aluminum open cell, and the temperature was measured in the range of 0 to 200 ° C. at a heating / cooling rate of 10 ° C./min. The endothermic behavior was judged from the DSC peak relative to the baseline of the DSC curve.

(Influence of heating / cooling rate)
Metallopolymers poly-NiL (Oc) Chl, poly-NiL (Dod) Chl, poly-NiL (Trd) Chl, poly-NiL (Ocd) Chl, and poly-NiL (Dod) -co-5% -NiL (UndCO _{For 2} H) Chl, the endothermic behavior was measured as follows, and the results are shown in FIGS.
The relationship between the heating / cooling rate and the amount of heat absorbed and exothermed was analyzed by changing the heating / cooling rate between 2 ° C./min and 40 ° C./min. From the results, the DSC peak area relative to the baseline of the DSC curve was defined as the amount of heat. When there were a plurality of peaks, the sum of all peak areas was defined as the amount of heat.
In addition, the amount of change in heat (ΔQ) relative to the change in heating / cooling rate is based on the amount of heat absorbed / generated at 2 ° C / min as a reference (1), after evaluating the amount of heat absorbed / generated at other heating / cooling rates. ΔQ was calculated from the slopes of these approximate lines.

(result)
(1) Absorption and heat generation were confirmed in any of the metallopolymers used. In particular, the metallopolymer poly-NiL (Dod) -co-5% -NiL (UndCO ₂ H) Chl with a functional group containing oxygen also absorbs and generates heat as seen in poly-NiL (Ocd) Chl. It could be confirmed.
(2) In the tests with different heating and cooling rates, in any of the metallopolymers used, the amount of change in heat with respect to the heating and cooling rate (ΔQ: slope of the approximate line) is ΔQ (exothermic)> ΔQ (endothermic). The relationship was recognized. That is, the supercooling effect was confirmed, and the heat storage effect of the ΔQ difference could be confirmed.

[Example 15]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and octylamine (258 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-dioctylimine. 2,6-Dihydroxynaphthalene-1,5-dioctylimine (44 mg) was dissolved in 10 mL of tetrahydrofuran, and a methanol solution of nickel acetate tetrahydrate separately prepared therein was mixed with the molar amount of ligand and metal ion. They were added so that the ratio was 1: 1. The dark red gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Oc) THF.

[Example 16]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and methylamine (62 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-dimethylimine. Dissolve 2,6-dihydroxynaphthalene-1,5-dimethylimine (24 mg) in 10 mL of tetrahydrofuran, and add a methanol solution of nickel acetate tetrahydrate prepared separately to the molarity of the ligand and metal ions. They were added so that the ratio was 1: 1. A yellowish brown powdery precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Me) THF.

[Example 17]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and isopropylamine (118 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-diisopropylimine. Dissolve 2,6-dihydroxynaphthalene-1,5-diisopropylimine (30 mg) in 10 mL of tetrahydrofuran, and add a methanol solution of nickel acetate tetrahydrate prepared separately to the ligand and metal ion moles. They were added so that the ratio was 1: 1. A yellowish brown powdery precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (i-Pr) THF.

[Example 18]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and tert-butylamine (146 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-ditert-butylimine. Dissolve 2,6-dihydroxynaphthalene-1,5-ditert-butylimine (33 mg) in 10 mL of tetrahydrofuran, and add a separately prepared methanol solution of nickel acetate tetrahydrate to the ligand and metal ions. Was added so that the molar ratio was 1: 1. A yellowish brown powdery precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (tert-Bu) THF.

[Example 19]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and pentylamine (176 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-dipentylimine. Dissolve 2,6-dihydroxynaphthalene-1,5-dipentylimine (35 mg) in 10 mL of tetrahydrofuran and add a separately prepared methanol solution of nickel acetate tetrahydrate to the molar ratio of ligand and metal ion. They were added so that the ratio was 1: 1. The dark red gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Pen) THF.

[Example 20]
2,6-Dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and hexylamine (202 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-dihexylimine. Dissolve 2,6-dihydroxynaphthalene-1,5-dihexylimine (38 mg) in 10 mL of tetrahydrofuran, and add a methanol solution of nickel acetate tetrahydrate separately prepared to the molar ratio of the ligand and metal ions. They were added so that the ratio was 1: 1. The dark red gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Hex) THF.

[Example 21]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and cetylamine (483 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-distilimine. Dissolve 2,6-dihydroxynaphthalene-1,5-dicetylimine (66 mg) in 10 mL of chloroform, and add a separately prepared methanol solution of nickel acetate tetrahydrate to the molar ratio of ligand to metal ion. Was added to become one to one. The dark red gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Cet) Chl.

[Example 22]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and benzylamine (214 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-dibenzylimine. 2,6-dihydroxynaphthalene-1,5-dibenzylimine (39 mg) was dissolved in 10 mL of tetrahydrofuran, and a methanol solution of nickel acetate tetrahydrate prepared separately was added to the ligand and metal ions. They were added so that the molar ratio was 1: 1. A yellowish brown gel-like precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Bn) THF.

[Example 23]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and R-1-phenethylamine (242 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-diR-1-phenethylimine. 2,6-Dihydroxynaphthalene-1,5-diR-1-phenethylimine (42 mg) was dissolved in 10 mL of tetrahydrofuran, and a separately prepared methanol solution of nickel acetate tetrahydrate was added to the ligand. And metal ions were added so that the molar ratio was 1: 1. A yellowish brown gel precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (R-PhE) THF.

[Example 24]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and S-1-phenethylamine (42 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-diS-1-phenethylimine. 2,6-dihydroxynaphthalene-1,5-diS-1-phenethylimine (42 mg) was dissolved in 10 mL of tetrahydrofuran, and a separately prepared methanol solution of nickel acetate tetrahydrate was added to the ligand. And metal ions were added so that the molar ratio was 1: 1. A yellowish brown gel-like precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (S-PhE) THF.

[Example 25]
2,6-dihydroxynaphthalene-1,5-dialdehyde (216 mg) was suspended in 20 mL of methanol, and picolylamine (216 mg) was added to the suspension. After stirring for 24 hours, the suspension was filtered to recover 2,6-dihydroxynaphthalene-1,5-dipicolyrimine. Dissolve 2,6-dihydroxynaphthalene-1,5-dipicolyrimin (40 mg) in 10 mL of chloroform, and add a separately prepared methanol solution of nickel acetate tetrahydrate to the molar ratio of ligand to metal ion. Was added to become one to one. A yellowish brown gel-like precipitate generated in the reaction solution was collected by filtration and dried under reduced pressure to obtain a metallopolymer poly-NiL (Pic) Chl.

[Example 26]
An appropriate amount of a metallopolymer poly-NiL (Oc) THF was taken in a case and sprayed onto a glass slide. A thin film was made by rubbing poly-NiL (Oc) THF on the glass surface on the back of the case. The thin film was observed with an optical microscope, and it was visually confirmed that the color tone of the thin film was dark red, and the transmitted light was introduced into the spectroscope through an optical fiber to record a spectral absorption spectrum. The spectrum is shown in FIG.

[Example 27]
An appropriate amount of a metallopolymer poly-NiL (Me) THF was taken in a shell and spread on a glass slide. A thin film was prepared by rubbing poly-NiL (Me) THF on the glass surface on the back of the shell. The thin film was observed with an optical microscope, and it was visually confirmed that the color tone of the thin film was tan, and the transmitted light was introduced into the spectroscope through an optical fiber, and a spectral absorption spectrum was recorded. The spectrum is shown in FIG.

[Example 28]
An appropriate amount of a metallopolymer poly-NiL (tert-Bu) THF was taken in a shell and spread on a glass slide. A thin film was prepared by rubbing poly-NiL (tert-Bu) THF on the glass surface on the back of the shell. The thin film was observed with an optical microscope, and it was visually confirmed that the color tone of the thin film was tan, and the transmitted light was introduced into the spectroscope through an optical fiber, and a spectral absorption spectrum was recorded. The spectrum is shown in FIG.

[Example 29]
An appropriate amount of a metallopolymer poly-NiL (Bn) THF was taken in a shell and spread on a glass slide. A thin film was made by rubbing poly-NiL (Bn) THF on the glass surface on the back of the shell. The thin film was observed with an optical microscope, and it was visually confirmed that the color tone of the thin film was tan, and the transmitted light was introduced into the spectroscope through an optical fiber, and a spectral absorption spectrum was recorded. The spectrum is shown in FIG.

[Example 30]
An appropriate amount of metallopolymer poly-NiL (Oc) THF was taken in a case and sprayed onto a 15 mmφ cover glass. A thin film was made by rubbing poly-NiL (Oc) THF on the glass surface on the back of the case. Set the cover glass on a temperature variable stage, observe the thin film with an optical microscope at 25 ° C, visually confirm that the color of the thin film is dark red, and introduce the transmitted light into the spectroscope with an optical fiber for spectroscopy. Absorption spectra were recorded. The stage was cooled to -180 ° C and then heated to + 180 ° C. The spectrum at each temperature is shown in FIG. In the spectrum at -180 ° C, the peak at a wavelength of 530 nm sharpened sharply compared to the spectrum at 25 ° C, but this peak shape hardly changed even when heated to 180 ° C.

[Example 31]
An appropriate amount of metallopolymer poly-NiL (Me) THF was taken in a case and sprayed onto a 15 mmφ cover glass. A thin film was prepared by rubbing poly-NiL (Me) THF on the glass surface on the back of the shell. Set the cover glass on a temperature variable stage, observe the thin film with an optical microscope at 25 ° C, visually confirm that the color of the thin film is dark red, and introduce the transmitted light into the spectroscope with an optical fiber for spectroscopy. Absorption spectra were recorded. The stage was cooled to -180 ° C and then heated to + 180 ° C. The spectrum at each temperature is shown in FIG. The spectrum at -180 ° C was not significantly different from that at 25 ° C. When heated to 180 ° C., the peak intensities at wavelengths of 480 nm and 500 nm decreased. When the temperature was lowered again to 25 ° C, the shape of the spectrum was restored to that of 25 ° C before the temperature change.

[Example 32]
An appropriate amount of metallopolymer poly-NiL (Bn) THF was taken in a case and sprayed onto a 15 mmφ cover glass. A thin film was made by rubbing poly-NiL (Bn) THF on the glass surface on the back of the shell. Set the cover glass on a temperature variable stage, observe the thin film with an optical microscope at 25 ° C, visually confirm that the color of the thin film is tan, and introduce the transmitted light into the spectroscope with an optical fiber. Absorption spectra were recorded. The stage was cooled to -180 ° C and then heated to + 180 ° C. The spectrum at each temperature is shown in FIG. The spectrum at -180 ° C was not significantly different from that at 25 ° C. When heated to 180 ° C., the peak intensity at a wavelength of 480 nm decreased and the 500 nm peak disappeared, while a sharp peak appeared at 530 nm. When the temperature was lowered to 25 ° C. again, the spectrum shape was not restored to that at 25 ° C. before the temperature change, and the spectra had peaks at 480 nm and 530 nm.

Matrix-Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) Method The matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS) of metallopolymers was performed using the following equipment and conditions.
(Assumption principle)
MALDI (Matrix-Assisted Laser Desorption / Ionization) is a kind of ionization method. When a sample and a matrix are mixed and irradiated with laser light, the matrix absorbs light and is excited. At this time, the sample is vaporized by the energy obtained from the matrix, and at the same time is ionized by reaction with the matrix and a salt added in advance. The generated ions fly in the flight tube and reach the detector. At that time, use the fact that the time to reach the detector (Time of Flight) differs according to the mass-to-charge ratio (m / z) (the ions with smaller m / z reach the detector earlier) Then, the ions are mass separated and detected. Since MALDI is a soft ionization method, mass information related to molecular weight can be easily obtained, and since monovalent ions are mainly generated, compared to ESI (Electrosplay Ionization), which easily generates multivalent ions. Analysis is also easy. Furthermore, since it is easy to ionize and a comparative sample is not selected, many compounds can be measured.

(Sample preparation)
Metallopolymer poly-NiL (Oc) THF is pulverized into powder in a mortar, and a small amount is placed on a measuring plate. A matrix reagent solution is applied on the plate, dried, and MALDI-TOF MS is measured. The results are shown in FIG. Indicated.
(Analysis equipment)
BRUKER DALTONICS, autoflex
(Measurement condition)
Laser light source: N ₂ laser (wavelength: 337 nm)
Measurement mode: reflector mode, positive ion mode Measurement mass range (m / z): 20-3000
Integration count: 1500 times Matrix: trans, trans-1,4-Diphenyl-1,3-butadiene (THF solution)

(Results and discussion)
From FIG. 33, it was found that monoisotopic peaks derived from samples were detected at m / z 438.3, 932.5, 1426.8, 1921.1, and 2415.4, and these ions were detected at 494 u intervals.
From the isotope pattern of ions, m / z 438.3, 932.5, 1426.8, 1921.1, and 2415.4 are considered to contain 0, 1, 2, 3, and 4 Ni atoms, respectively, and 494 u contains Ni atoms. Thought to contain one.
From these, the molecular weight of the ligand R of Ni is 437, m / z 438.3 is RH +, 932.5 is [R-Ni-R] +, 1426.8 is [R-Ni-R-Ni-R ] + ・, 1921.1 is estimated as [R-Ni-R-Ni-R-Ni-R] + ・, 2415.4 is estimated as [R-Ni-R-Ni-R-Ni-R-Ni-R] + ・It was.
Further, n of the metallopolymer poly-NiL (Oc) THF was found to be 4.

  As shown in the above examples, the sample obtained by applying the metallopolymer of the present invention on a substrate to form a thin film was observed under a microscope and subjected to spectroscopic analysis. As a result, the absorption spectrum in the UV-visible region shows temperature dependence. It was recognized that It has also been found that spectral changes are reversible and irreversible with temperature changes, depending on the type of alkylamine used. In the examples, the metallopolymer of the present invention is brought into contact with a heat source and the color change is observed, which can be interpreted as an experiment of a heat storage system. The metallopolymer of the present invention has both a reversible system and an irreversible system with respect to temperature change, and shows that the thermochromism mechanism of the metallopolymer of the present invention does not involve decomposition of the metallopolymer. Yes. It can be understood that the temperature is a strong state quantity, and the same phenomenon can occur even when scaled up, and that the metallopolymer of the present invention has a heat storage effect, taking into account the first law of thermodynamics.

  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 (7)

Formula (I):

[In the formula, each R is independently a linear or branched alkyl group having 1 to 18 carbon atoms, wherein the alkyl group is unsubstituted or represents —OH, —C ( _{= O) OH, -O-C} (= O) H, -NH 2, = NH, -NHC (= O) H, -C (= O) NH 2, or is substituted with an aromatic ring, and / Alternatively, the alkyl group has —CH═CH—, —C≡C—, —O—, —C (═O) O—, —O—C (═O) —, —NH—, in the middle of the alkyl chain. ═N—, —N═, —NHC (═O) —, or —C (═O) NH—; M is a divalent transition metal ion]. Characteristic heat storage material.   The heat storage material according to claim 1, wherein R is octyl, tridecyl, or octadecyl.   The heat storage material according to claim 1 or 2, 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 3, wherein the divalent transition metal ion is zinc (II), copper (II), nickel (II), cobalt (II), manganese (II), or iron (II).   The waste heat utilization system provided with the heat storage material of any one of Claims 1-4.   The exhaust heat utilization system according to claim 5, which is a vehicle exhaust heat utilization system.   The exhaust heat utilization system according to claim 5, which is a residential exhaust heat utilization system.