JP2021172730A - Heat storage material - Google Patents

Abstract

To provide a heat storage material containing an organic ion-pair compound and having a high heat storage density.SOLUTION: The heat storage material contains a nitrogen-containing ion-pair compound represented by the following formula (1). R1 represents a C1-12 carbon chain CCA, -H, -OH, -NH2, or a substituted carbon chain SCA obtained by substituting one or more H atoms constituting the carbon chain CCA with one or more selected from -OH, -OMe and -NH2; R2-R4 each represent a C1-12 carbon chain CCB, -OH, -NH2, or a substituted carbon chain SCB obtained by substituting one or more H atoms constituting the carbon chain CCB with one or more selected from -OH, -OMe and -NH2; and X- represents Br-, Cl- or the like.SELECTED DRAWING: Figure 1

Description

The present invention relates to a heat storage material.

Conventionally, a latent heat storage material using a heat absorption phenomenon accompanying a phase change of a material is known. Hereinafter, the latent heat storage material is simply referred to as a "heat storage material".

_{The heat storage material has a melting point T m} , which is the temperature at which the crystalline solid melts when heated to become _{an isotropic liquid, and a freezing point T s} , which is the temperature at which the isotropic liquid solidifies when the isotropic liquid is cooled. Have. Incidentally, the heat storage material, depending on the type, resulting in supercooling phenomenon solidifies at a temperature lower than the freezing point T _s during cooling.

The heat storage material preferably has _{a melting point T m in} the temperature range of the target in which the heat storage material is used. For example, when the heat storage material utilizes automobile waste heat, factory waste heat, or the like, a heat storage material having a _{melting point T m at 40 to 200 ° C. is required from the viewpoint of effective utilization of these waste heats.} Further, the heat storage material preferably has a high heat storage density (heat storage amount) from the viewpoint of miniaturization of the heat storage material.

Further, in the heat storage material, if supercooling does not occur or the degree thereof is small, a phase change with respect to a temperature change occurs rapidly, which is preferable.

Conventionally, a technique for reducing the degree of supercooling of a heat storage material has been proposed. Patent Document 1 discloses a heat storage material containing a specific ammonium salt (A).

Japanese Unexamined Patent Publication No. 2008-120871

However, the heat storage material of Patent Document 1 has a problem that the heat storage density of the organic ion pair compound itself, which is the main component of the heat storage material, excluding the shell is low.

The present invention has been made in view of the problems of the prior art. An object of the present invention is to provide a heat storage material containing an organic ion pair compound and having a high heat storage density.

（式中、
Ｒ^１は、炭素数１〜１２の炭素鎖ＣＣ^Ａ、−Ｈ、−ＯＨ、−ＮＨ_２、又は、前記炭素鎖ＣＣ^Ａを構成するＨの１個以上が−ＯＨ、−ＯＭｅ及び−ＮＨ_２から選ばれる１種以上で置換された置換炭素鎖ＳＣ^Ａであり；
Ｒ^２〜Ｒ^４は、炭素数１〜１２の炭素鎖ＣＣ^Ｂ、−ＯＨ、−ＮＨ_２、又は、前記炭素鎖ＣＣ^Ｂを構成するＨの１個以上が−ＯＨ、−ＯＭｅ及び−ＮＨ_２から選ばれる１種以上で置換された置換炭素鎖ＳＣ^Ｂであり；
Ｘ⁻は、Ｂｒ⁻、Ｃｌ⁻、ビス（トリフルオロメタンスルホニル）イミドイオン、ヘキサフルオロリン酸イオン、トリフルオロメタンスルホン酸イオン、メタンスルホン酸イオン、テトラフェニルホウ酸イオン、又はテトラフルオロホウ酸イオンである。） The heat storage material according to the aspect of the present invention is represented by the following formula (1) and contains a nitrogen-containing ion pair compound that is not an aromatic compound.

(During the ceremony,
In R ^{1 , one or more of carbon chains CC A} , -H, -OH, -NH ₂ having 1 to 12 carbon atoms, or H constituting the carbon chain CC ^A are -OH, -OMe and -NH ₂ ^{Substituent carbon chain SC A} substituted with one or more selected from;
R ² to R ⁴ is a carbon chain ^CC B of 1 to 12 carbon atoms, -OH, -NH _2, or, one or more -OH of H constituting the carbon chain CC ^B, -OMe and -NH ₂ a substituted carbon chain SC ^B substituted with one or more selected from;
X ⁻ is Br ⁻ , Cl ⁻ , bis (trifluoromethanesulfonyl) imide ion, hexafluorophosphate ion, trifluoromethanesulfonic acid ion, methanesulfonic acid ion, tetraphenylborate ion, or tetrafluoroborate ion. )

It is preferable that R ^{1 to} R ⁴ are linear, respectively.

It is preferable that at least one of R ^{1 to} R ^{4 contains -OH.}

The nitrogen-containing ion pair compound is preferably represented by the following formula (1La).

The heat storage material preferably does not contain a supercooling inhibitor.

According to the present invention, it is possible to provide a heat storage material containing an organic ion pair compound and having a high heat storage density.

This is an example of a DSC (differential scanning calorimetry) curve including a peak P _{m of} heat of fusion and a peak P _{s of heat of solidification.}

Hereinafter, the heat storage material according to the embodiment of the present invention will be described in detail with reference to the drawings.

[Heat storage material]
The heat storage material according to the present embodiment is represented by the following formula (1) and contains a nitrogen-containing ion pair compound that is not an aromatic compound.

（式中、
Ｒ^１は、炭素数１〜１２の炭素鎖ＣＣ^Ａ、−Ｈ、−ＯＨ、−ＮＨ_２、又は、前記炭素鎖ＣＣ^Ａを構成するＨの１個以上が−ＯＨ、−ＯＭｅ及び−ＮＨ_２から選ばれる１種以上で置換された置換炭素鎖ＳＣ^Ａであり；
Ｒ^２〜Ｒ^４は、炭素数１〜１２の炭素鎖ＣＣ^Ｂ、−ＯＨ、−ＮＨ_２、又は、前記炭素鎖ＣＣ^Ｂを構成するＨの１個以上が−ＯＨ、−ＯＭｅ及び−ＮＨ_２から選ばれる１種以上で置換された置換炭素鎖ＳＣ^Ｂであり；
Ｘ⁻は、Ｂｒ⁻、Ｃｌ⁻、ビス（トリフルオロメタンスルホニル）イミドイオン、ヘキサフルオロリン酸イオン、トリフルオロメタンスルホン酸イオン、メタンスルホン酸イオン、テトラフェニルホウ酸イオン、又はテトラフルオロホウ酸イオンである。）

(During the ceremony,
In R ^{1 , one or more of carbon chains CC A} , -H, -OH, -NH ₂ having 1 to 12 carbon atoms, or H constituting the carbon chain CC ^A are -OH, -OMe and -NH ₂ ^{Substituent carbon chain SC A} substituted with one or more selected from;
R ² to R ⁴ is a carbon chain ^CC B of 1 to 12 carbon atoms, -OH, -NH _2, or, one or more -OH of H constituting the carbon chain CC ^B, -OMe and -NH ₂ a substituted carbon chain SC ^B substituted with one or more selected from;
X ⁻ is Br ⁻ , Cl ⁻ , bis (trifluoromethanesulfonyl) imide ion, hexafluorophosphate ion, trifluoromethanesulfonic acid ion, methanesulfonic acid ion, tetraphenylborate ion, or tetrafluoroborate ion. )

As the nitrogen-containing ion pair compound represented by the formula (1), a linearly bound nitrogen-containing ion pair compound is used. Here, the linearly bound nitrogen-containing ion pair compound means a linearly bound nitrogen-containing ion pair compound in which R ^{1 to} R ⁴ are linear, respectively. ^{It is preferable that R 1 to} R ⁴ of the nitrogen-containing ion pair compound represented by the formula (1) are linear, because the heat storage density of the heat storage material tends to be high.

The nitrogen-containing ion pair compound represented by the formula (1) is preferable when ^{one or more of R 1 to} R ⁴ contains -OH because the heat storage density of the heat storage material tends to be high. Further, the larger the amount of −OH in the nitrogen-containing ion pair compound represented by the formula (1), the higher the heat storage density of the heat storage material is likely to be, which is more preferable.

(Linear-bonded nitrogen-containing ion pair compound)
As the linearly bound nitrogen-containing ion pair compound, for example, those shown below are used.

テトラ（デシル）アンモニウムブロミド

Tetra (decyl) ammonium bromide

The substance represented by (A6) is preferable in that the heat storage density at the melting point exceeds 100 J / g and there is no supercooling behavior.

テトラペンチルアンモニウムブロミド

Tetrapentyl ammonium bromide

The substance represented by (A13) is preferable in that the heat storage density at the melting point exceeds 100 J / g and there is no supercooling behavior.

臭化テトラエタノールアンモニウム

Tetraethanol ammonium bromide

The substance represented by (A15) is preferable in that the heat storage density at the melting point exceeds 100 J / g and there is no supercooling behavior.

The nitrogen-containing ion pair compound is preferably represented by the following formula (1La) because it has the highest heat storage density at the melting point exceeding 100 J / g and does not have supercooling behavior. The substance represented by the following formula (1La) is the same as the substance represented by the above formula (A15).

The supercooling phenomenon is unlikely to occur in the nitrogen-containing ion pair compounds (A1), (A3), (A4), (A6), (A7), (A9) to (A17), (A19), and (A22). Therefore, these nitrogen-containing ion pair compounds can be free of supercooling inhibitors.

(Characteristic)
Heat storage material according to the present embodiment, it is possible to make the melting point T _m in the range of 40 to 200 ° C.. When the melting point T _m of a heat storage material is in the range of 40 to 200 ° C., preferably for a good efficiency of use of an automobile exhaust heat or factory waste heat.

The heat storage material according to the present embodiment can have a heat storage density H _{m at a melting point T m} of 100 J / g or more. When the heat storage density H _m at the melting point T _m of a heat storage material is 100 J / g or more, increasing the persistence of the effect of the heat storage material, also preferred because it contributes to miniaturization of the apparatus using the heat storage material.

(effect)
According to the heat storage material according to the present embodiment, it is possible to provide a heat storage material containing an organic ion pair compound and having a high heat storage density.

Further, according to the heat storage material according to the present embodiment, the heat storage density is adjusted by having the molecular structure of the nitrogen-containing ion pair compound represented by the formula (1) as the basic structure and adjusting the entire molecular structure. It is possible to adjust.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
[Examples and Comparative Examples]
(Preparation or acquisition of substances shown in Tables 1 and 2)
The substances shown in Tables 1 and 2 were prepared or obtained (Sample Nos. A1 to A23). Structural formula No. in Tables 1 and 2. The structural formula corresponding to is described later. The substances shown in Tables 1 and 2 can be obtained by known methods, and production examples of some substances will be described later.

Sample Nos. The structural formulas of A1 to A23 are as follows.

酢酸コリン

Choline acetate

テトラメチルアンモニウムテトラフェニルホウ酸

Tetramethylammonium tetraphenylborate

テトラブチルアンモニウムテトラフェニルホウ酸

Tetrabutylammonium tetraphenylborate

テトラエチルアンモニウムテトラフェニルホウ酸

Tetraethylammonium tetraphenylborate

テトラメチルアンモニウムブロミド

Tetramethylammonium bromide

テトラ（デシル）アンモニウムブロミド

Tetra (decyl) ammonium bromide

コリンブロミド

Colin bromide

テトラブチルアンモニウムブロミド

Tetrabutylammonium bromide

テトラヘキシルアンモニウムブロミド

Tetrahexyl ammonium bromide

テトラ−ｎ−オクチルアンモニウムブロミド

Tetra-n-octylammonium bromide

テトラドデシルアンモニウムブロミド

Tetradodecyl ammonium bromide

テトラ−ｎ−オクチルメチルアンモニウムブロミド

Tetra-n-octylmethylammonium bromide

テトラペンチルアンモニウムブロミド

Tetrapentyl ammonium bromide

テトラエチルアンモニウムブロミド

Tetraethylammonium bromide

臭化テトラエタノールアンモニウム

Tetraethanol ammonium bromide

ビス（２−ヒドロキシエチル）ジメチルアンモニウムクロリド

Bis (2-hydroxyethyl) dimethylammonium chloride

コリンクロリド

Choline chloride

メチルトリオクチルアンモニウムヘキサフルオロリン酸塩

Methyltrioctyl ammonium hexafluorophosphate

ヘキサフルオロリン酸テトラブチルアンモニウム

Tetrabutylammonium hexafluorophosphate

トリブチルメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド

Tributylmethylammonium = bis (trifluoromethanesulfonyl) imide

ブチルトリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド

Butyltrimethylammonium = bis (trifluoromethanesulfonyl) imide

トリメチルプロピルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド

Trimethylpropylammonium = bis (trifluoromethanesulfonyl) imide

トリメチルヘキシルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド

Trimethylhexylammonium = bis (trifluoromethanesulfonyl) imide

Hereinafter, production examples of some substances will be shown.

(A15: Production example of tetraethanolammonium bromide)
40 ml of methyl acetate and 2.95 g of tris (hydroxyethyl) amine were placed in a 100 ml round bottom flask and mixed at room temperature for 5 minutes. 2.05 ml of 2-bromoethinol was added dropwise to this mixture. After the dropwise addition, 27 ml of ethyl acetate was further added, and the mixture was heated under reflux for 17 hours and cooled to room temperature to obtain a reaction solution containing crystals. Methanol was added to this reaction solution, the solvent was distilled off until it became about 5 ml, and 10 ml of ethyl acetate and 50 ml of methanol were added again. After filtering this mixed solution with a filter paper, the solvent was distilled off until it became about 5 ml, and crystals were formed in the mixed solution. Crystals were obtained by filtering this mixed solution with a filter paper, and the crystals were washed with 5 ml of ethyl acetate and dried to obtain a white powder.

The reaction formula is shown below.

(A2: Example of production of tetramethylammonium tetraphenylborate)
0.31 g of tetramethylammonium bromide was placed in a 50 ml round bottom flask, and 20 ml of methanol and 0.63 g of sodium tetraphenylborate were added and dissolved. Stirring at room temperature for 18 hours gave a suspension. When this suspension was washed with 50 ml of methanol, 0.71 g of white powder was obtained. The yield was 92%.

The reaction formula is shown below.

(A4: Production example of tetramethylammonium tetraphenylborate)
0.31 g of tetraethylammonium bromide was placed in a 50 ml round bottom flask, and 15 ml of methanol and 0.46 g of sodium tetraphenylborate were added and dissolved. Stirring at room temperature for 18 hours gave a suspension. When this suspension was washed with 50 ml of methanol, 0.59 g of white powder was obtained. The yield was 92%.

The reaction formula is shown below.

(evaluation)
For each sample, the following DSC measurement, the melting point _{T m,} the thermal storage density _H m (J / g) at the melting point _{T m,} was measured total thermal storage density _H T (J / g). The total thermal storage density H _T, and the thermal storage density in the entire measurement range of the DSC. Since the measurement range of the DSC is -80 ° C. to 250 DEG ° C. as follows, all heat storage density _{H T} is the thermal storage density at -80 ° C. to 250 DEG ° C.. The specific DSC measurement is as follows.

(DSC measurement)
5 mg of sample was placed on an aluminum pan. The aluminum pan on which this sample was placed and the blank aluminum pan on which the sample was not placed were placed on the measurement site of the DSC device DSC3 + manufactured by METTLER TOKRY CORPORATION. Next, under a nitrogen atmosphere, heating at 10 ° C./min and cooling at −10 ° C./min were repeated in the range of −80 ° C. to 250 ° C.
FIG. 1 is an example of a DSC (differential scanning calorimetry) curve including _{a peak P m of} heat of fusion and a peak P _{s of heat of solidification.} Specifically, FIG. 1 shows the sample No. It is a DSC curve of A15.
The temperature of the peak P _m of the heat of fusion was defined as the melting point T _m , and the temperature of the peak P _s of the heat of fusion was defined as the freezing point T _s . The freezing point T _s is not shown in the table. Also, the area of the peak _{P m} of heat of fusion, using a melting point _{T m,} was measured thermal storage density _{H m,} and the total thermal storage density _{H T} at the melting point _{T m.}
These results are shown in Tables 1 and 2.

(Supercooling behavior)
The supercooling behavior was measured as follows.
In the DSC curve, Ps as shown in FIG. 1 does not appear at the time of cooling, solidifies for the first time at the time of subsequent heating, the peak Ps of the heat of solidification appears, and when the temperature rises further, it melts and the peak Pm of the heat of fusion appears. It was determined that the supercooling behavior was "yes". Further, as shown in FIG. 1, the supercooling behavior was judged to be "none" when the peak Ps of the heat of solidification appeared at the time of cooling and the peak Pm of the heat of fusion appeared at the time of heating.

From Table 1 and Table 2, the following was found.
Sample No. A1, A6~A15, A17, A18 has a melting point _{T m} is in the range of 40 to 200 ° C..
Sample No. A6, A13, and A15 have a heat storage density H _{m at a melting point T m} of 100 J / g or more.
Sample No. A1, A3, A4, A6, A7, A9 to A17, A19, and A22 have no supercooling behavior.

Although the present embodiment has been described above, the present embodiment is not limited to these, and various modifications can be made within the scope of the gist of the present embodiment.

The heat storage material according to the present embodiment can be used, for example, in building materials, refrigerators / freezers, ice packs, heat insulating materials, automobiles, hot water storage equipment, factories, and the like. Specifically, the heat storage material according to the present embodiment can be used as a heat storage material that utilizes waste heat from automobiles or waste heat from factories, and more specifically, waste heat from automobiles at 40 to 200 ° C. or factories. It can be used as a heat storage material that utilizes waste heat and the like.

P _m heat of fusion peak P _s solidification heat peak

Claims (5)

A heat storage material represented by the following formula (1) and containing a nitrogen-containing ion pair compound that is not an aromatic compound.

(During the ceremony,
In R ^{1 , one or more of carbon chains CC A} , -H, -OH, -NH ₂ having 1 to 12 carbon atoms, or H constituting the carbon chain CC ^A are -OH, -OMe and -NH ₂ ^{Substituent carbon chain SC A} substituted with one or more selected from;
R ² to R ⁴ is a carbon chain ^CC B of 1 to 12 carbon atoms, -OH, -NH _2, or, one or more -OH of H constituting the carbon chain CC ^B, -OMe and -NH ₂ a substituted carbon chain SC ^B substituted with one or more selected from;
X ⁻ is Br ⁻ , Cl ⁻ , bis (trifluoromethanesulfonyl) imide ion, hexafluorophosphate ion, trifluoromethanesulfonic acid ion, methanesulfonic acid ion, tetraphenylborate ion, or tetrafluoroborate ion. ) The heat storage material according to claim 1, wherein ^{each of R 1 to} R ^{4 is linear.} The heat storage material according to claim 1 or 2, wherein ^{one or more of R 1 to} R ^{4 contains -OH.} The heat storage material according to any one of claims 1 to 3, wherein the nitrogen-containing ion pair compound is represented by the following formula (1La).

The heat storage material according to any one of claims 1 to 4, which does not contain a supercooling inhibitor.

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