WO2019123914A1

WO2019123914A1 - Chemical heat storage complex, composition for forming chemical heat storage complex, and method for forming chemical heat storage complex

Info

Publication number: WO2019123914A1
Application number: PCT/JP2018/042260
Authority: WO
Inventors: 隆一清岡; 真矢田; 義之佐野; 香河村
Original assignee: Dic株式会社
Priority date: 2017-12-21
Filing date: 2018-11-15
Publication date: 2019-06-27
Also published as: JP6863481B2; JPWO2019123914A1

Abstract

Provided is a chemical heat storage complex which cannot be separated from a heat exchanger upon the occurrence of volume expansion of a heat storage material or the like and can withstand repeated use. A chemical heat storage complex comprising an elastomer having a chemical crosslinked structure and a chemical heat storage material. As a liquid capable of being cured upon heating, a liquid capable of generating at least one resin selected from the group consisting of a silicone resin, a polyester resin, an epoxy resin and a urethane resin can be used preferably. In the use in combination with a heat exchanger, the chemical heat storage complex according to the present invention can be used suitably as a waste heat utilization system for factories, a waste heat utilization system for vehicles, a heat utilization system for residential use (e.g., an air conditioning system) or the like.

Description

Chemical heat storage composite, composition for forming chemical heat storage composite, and method for forming chemical heat storage composite

The present invention relates to a chemical heat storage composite including a resin and a chemical heat storage material.

In recent years, in order to use energy efficiently, establishment of heat energy storage technology and heat storage technology using exhaust heat has been required. As a heat storage system currently put into practical use, there is a system using sensible heat or latent heat using a heat storage medium. However, these systems have a low heat storage capacity, and require a heat insulating material for heat retention, and are not suitable for long-term heat storage storage. Chemical thermal storage has attracted attention as a method for solving these problems.

In chemical thermal storage, chemical thermal storage materials such as metal oxides, salts, and adsorbents, and reaction medium gases such as water, ammonia, and methanol reversibly react chemically or adsorbate, and store heat and generate exothermic reactions by endothermic reaction. It is a heat storage system that dissipates heat. Such chemical heat storage has a large heat storage amount compared with the latent heat and the sensible heat which are other heat storage methods, and has the advantage of being able to store heat stably for a long period of time because it is not necessary to keep warm. Chemical thermal storage materials are used in chemical thermal storage systems such as chemical heat pumps where effective use of thermal energy is required. Using this chemical heat storage system, cold heat is created from exhaust heat of 100 ° C. or less emitted from a car, and studies are being conducted to improve the fuel efficiency of the car as an air conditioner system.

The chemical heat storage material is used, for example, by being packed in a heat exchanger. However, when using a chemical thermal storage material as powder, the volume of the chemical thermal storage material expands and contracts in the process of repeating heat absorption and exothermic reaction, and the chemical thermal storage material drops out of the heat exchanger, resulting in a decrease in the amount of thermal storage. was there.

Various studies have been conducted on such problems. For example, there is disclosed a method of supporting a chemical thermal storage material on a cage-like carbon structure having a large number of holes by bringing a hardly volatile organic substance and a chemical thermal storage material into contact and firing under an inert atmosphere (Patent Literature 1). In addition, the chemical thermal storage medium is included in the dense three-dimensional structure formed by desorbing all the alkoxy groups bonded to silicon by baking the alkoxysilane at 680 ° C. or more, the chemical thermal storage medium is broken. A method for prevention is disclosed (US Pat. In addition, a method of preventing leakage of the heat storage material is considered by using a core-shell structure having a heat storage material including a chemical heat storage material as a core and a polyurethane polyurea having a high mechanical strength as a shell.
JP, 2009-256518, A JP, 2015-098582, A JP 2017-137437 A

However, in the methods of Patent Documents 1 and 2, the structure becomes hard and brittle because it is a method of obtaining a three-dimensional structure surrounding the heat storage material by firing, and the heat exchanger can not follow the volume expansion of the chemical heat storage material. There is a fact that we can not suppress dropout from Further, in the method of Patent Document 3, the shell portion is provided with a function to prevent volatilization and exudation, so there is a problem that the chemical heat storage material and the reaction medium gas can not sufficiently react with each other.

In view of the above-mentioned situation, the problem to be solved by the present invention is to provide a chemical heat storage composite which can stand off from the heat exchanger due to volumetric expansion of the heat storage material and can endure repeated use. .

In order to solve the fundamental problem, it was conceived to reduce the stress at the time of volumetric expansion of the chemical heat storage material, and as a result of earnestly examining, by carrying the chemical heat storage material on a specific resin, it is possible to relieve the stress. The present invention has been achieved.

That is, the present invention relates to the following items 1 to 6.
Item 1.
What is claimed is: 1. A chemical heat storage composite comprising: a chemical heat storage composite containing an elastomer having a chemical crosslink structure and a chemical heat storage material.
Item 2.
A chemical heat storage composite characterized in that it is a chemical heat storage composite having a bulk density of 1.0 to 6.0 g / cm ³ , containing an elastomer having a chemical crosslink structure and a chemical heat storage material.
Item 3.
3. The elastomer according to item 1 or 2, wherein the elastomer is at least one resin selected from the group consisting of natural rubber, diene rubber, olefin rubber, silicone resin, polyester resin, epoxy resin and urethane resin. Chemical heat storage complex.
Item 4.
A composition for forming a chemical thermal storage composite, comprising a liquid that is cured by heating and a chemical heat storage material, wherein the liquid that is cured by the heating becomes an elastomer when it is cured. Composition for chemical thermal storage complex formation.
Item 5.
A composition for forming a chemical thermal storage composite, comprising a liquid that cures by heating, and a chemical heat storage material, wherein the liquid that cures by heating becomes an elastomer when cured, and after curing A composition for forming a chemical heat storage composite, wherein the chemical heat storage composite is prepared to have a bulk density of 1.0 to 6.0 g / cm ³ .
Item 6.
6. The composition for forming a chemical heat storage composite according to item 4 or 5, further comprising a solvent.
Item 7.
7. The elastomer according to any one of claims 4 to 6, wherein the elastomer is at least one resin selected from the group consisting of natural rubber, diene rubber, olefin rubber, silicone resin, polyester resin, epoxy resin and urethane resin. The composition for chemical thermal storage composites formation as described in a term.
Item 8.
Item 8. A step of applying the composition for forming a chemical heat storage composite according to any one of items 4 to 7 on the surface of a substrate, and a step of heating the substrate on which the composition for forming a chemical heat storage composite is applied And a method of forming a chemical thermal storage complex.

The chemical thermal storage composite of the present invention is excellent in heat storage density per volume, and can repeat volumetric expansion of a chemical thermal storage medium contained in the composite even if heat absorption and exothermic reaction are repeated. For this reason, the chemical heat storage composite of the present invention has an excellent effect of having a high heat storage density and having a long life. Moreover, according to the composition for chemical thermal storage complex formation of this invention, when a chemical thermal storage complex is formed using this, the chemical thermal storage complex which exhibits the above outstanding effects can be obtained.

The chemical thermal storage composite in the present invention is a composite material (sometimes referred to as a thermal storage material in the present specification) composed of a resin that is an elastomer having a chemical cross-linked structure and a chemical thermal storage material. The chemical heat storage material is dispersed in the resin and is contained in the resin. Since the resin is an elastomer having a chemically cross-linked structure, the resin has a rubber-like structure and is an easy-to-stretch (soft) material. Therefore, by taking such a structure, it is possible to relieve the stress at the time of volumetric expansion and contraction of the chemical thermal storage material which occurs at the time of heat storage and heat radiation by the resin, and it is possible to prevent deterioration of the chemical thermal storage material. Further, the elastomer having a chemically crosslinked structure has high heat resistance, and can maintain a sufficient rubber-like structure even after repeated use, so that the life of the chemical heat storage material can be extended.

Elastomers having a chemically crosslinked structure are known to have high gas permeability, and even if a chemical heat storage material is contained in the resin, it can react with the reaction medium gas.
Since the reaction between the chemical heat storage material and the reaction medium gas is also fully considered and designed, providing a void in the support structure is not an essential condition for functioning, so the heat storage density can be improved. It is. As a result, the above excellent effects can be obtained.

Hereinafter, the present invention will be described in detail.
<Description of chemical heat storage complex>
In the present invention, the term "chemical heat storage composite" refers to a composite of a chemical heat storage material and a resin. The “chemical heat storage material” described later is different. In addition, the "composition for chemical thermal storage composites" mentioned later is a material used for formation of a chemical thermal storage composite, and it can form it by the below-mentioned method etc.

<Description of Elastomer>
The elastomer used in the present invention is characterized by being an elastomer having a chemically crosslinked structure. The elastomer having a chemically crosslinked structure is one obtained by covalently crosslinking a soft segment or a soft segment and a hard segment. By having such a chemical crosslinked structure, the stress in the volume change of the expansion and contraction required for the chemical heat storage composite can be relaxed, and the technical failure in the case where the stress is not relieved can be solved. The hard segment in the elastomer is not particularly limited, and examples thereof include polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide and the like. Although the soft segment is not particularly limited, for example, polybutadiene, polyisoprene, polyisobutylene, aliphatic polyester, aliphatic polyether, polydimethylsiloxane, polyvinylidene fluoride, ethylene / propylene / diene rubber, ethylene / propylene rubber, acrylic rubber, Fluorine rubber, silicone rubber and the like can be mentioned. Each segment may be of one type or a combination of two or more types.
The crosslinking is not particularly limited. For example, crosslinking with sulfur or sulfur compound (vulcanization), crosslinking with epoxy group, crosslinking with isocyanate and alcohol (urethane bond), crosslinking with peroxide, crosslinking by hydrosilylation reaction, dehydration Crosslinking by condensation and the like can be mentioned. The crosslinking method is not particularly limited, and examples thereof include crosslinking by heating, crosslinking by ultraviolet light, and crosslinking by radiation. Crosslinking by heating is preferred from the viewpoint of productivity.
Although it does not specifically limit as an elastomer which has a chemical crosslinking structure, For example, natural rubber, diene system rubber, olefin system rubber, silicone resin, polyester resin, epoxy resin, urethane resin, urethane rubber, fluororubber, silicone rubber etc. are mentioned. Be Natural rubber, diene-based rubber, and rubber such as olefin-based rubber are not preferable because time and effort such as mastication and viscosity adjustment are separately required before crosslinking such as vulcanization. Silicone resins, polyester resins, epoxy resins, and so on because they can be combined with ease of obtaining raw materials, better processability and durability (heat resistance, light resistance, chemical resistance, etc.) and gas permeability and productivity as described below. Urethane resin is preferred. The resin having such a suitable chemical cross-linking structure is also attached to the heat exchanger in actual use, and when the endothermic reaction and the exothermic reaction are repeated, the chemical heat storage material falls off from the chemical heat storage composite. Can be suppressed for a longer period of time.

From the viewpoint of gas permeability and productivity, the elastomer having a chemically crosslinked structure preferably has a glass transition temperature of -140 ° C. or more and 30 ° C. or less, and an elastic modulus of 30 MPa or more and 0.3 MPa or more and 500 MPa or less It is preferable to be in the range of The glass transition temperature and the elastic modulus used the value calculated | required by the following evaluation methods.

<Evaluation of glass transition temperature of elastomer>
The glass transition temperature of the elastomer in the chemical heat storage composite can be measured by a dynamic viscoelasticity measurement device, and the temperature of the maximum value of the loss tangent (tan δ) obtained by the measurement is taken as the glass transition temperature. In the measurement, a strip-shaped chemical thermal storage composite was measured with a dynamic viscoelasticity measuring device under conditions of a temperature elevation temperature of 3 ° C./min and a frequency of 1 Hz. The loss tangent (tan δ) is the value obtained by dividing the loss modulus (E ′ ′) by the storage modulus (E ′) (tan δ = E ′ ′ / E ′).

<Evaluation of elastic modulus of elastomer>
It is difficult to measure only the elastic modulus of the elastomer from the chemical thermal storage composite, and it was obtained by curing the liquid that cures by heating, excluding the chemical thermal storage material, in the composition for forming a chemical thermal storage composite. The elastic modulus of the elastomer was taken as the elastic modulus of the elastomer in the chemical heat storage composite. The elastic modulus of the elastomer was taken as the storage elastic modulus (E ') when the resin was measured at a temperature of 30 ° C. and a frequency of 1 Hz by a dynamic viscoelasticity measuring device.

<Description of chemical heat storage material>
The chemical heat storage material used in the present invention reversibly chemically reacts or adsorbs with the reaction medium gas, and is capable of storing heat as an endothermic reaction and releasing heat as an exothermic reaction. Examples of the chemical heat storage material include metal oxides, hydroxides, salts, and adsorbents.

Specific examples of the reaction medium gas include gases such as water (steam), ammonia, hydrogen, carbon dioxide, alcohols, ammonia, primary amines, secondary amines, and tertiary amines. The reaction medium may be used alone or in combination of two or more. Alcohols include methanol, ethanol, 1-propanol, 2-propanol, n-butanol, ethylene glycol and the like. Examples of primary amines include methylamine, ethylamine and propylamine. Examples of secondary amines include dimethylamine, ethylmethylamine, N-methylpropylamine and the like. Examples of tertiary amines include trimethylamine, N, N-diethylmethylamine, N, N-dimethylethylamine and the like. For example, water (steam), ammonia, carbon dioxide, methanol, and ethanol are preferable from the viewpoint of excellent stability in repetition of heat storage and heat release when the chemical heat storage composite is used by being incorporated into a heat exchanger. A preferred reaction medium gas with less hazard and ease of handling and relatively high heat removal is water (steam).

A chemical heat storage material suitable for the reaction medium gas can be appropriately selected. Any of known and commonly used chemical heat storage materials can be used. In a preferred embodiment, for example, in the case of the reaction between a chemical heat storage material and water (steam), the reaction between the chemical heat storage material and water (steam) is a hydration reaction, an adsorption reaction of water molecules, a hydroxylation reaction, etc. Can be mentioned. An example of the reaction is shown below. In the hydration reaction, heat is generated upon hydration with water (steam), and endotherm occurs upon dehydration. In the adsorption reaction of water molecules, heat is generated when the water molecules are adsorbed to the heat storage material, and heat absorption occurs when dewatering. In the hydroxylation reaction, heat is generated when water (steam) and the oxide undergo a hydration reaction to form a hydroxide, and an endothermic reaction occurs at the time of a dehydration reaction to form water (steam) and the oxide from the hydroxide.

Hydration reaction
CaCl ₂ + nH ₂ O ⇔ CaCl ₂ · nH ₂ O
LiOH + H ₂ O ⇔ LiOH · H ₂ O
Ba (OH) ₂ + nH ₂ O ⇔ Ba (OH) ₂ · nH ₂ O

Adsorption and desorption reactions of water molecules
Zeolite + nH ₂ O ⇔ Zeolite n H ₂ O

Hydroxylation reaction
MgO + H ₂ O Mg Mg (OH) ₂
CaO + H ₂ O ⇔ Ca (OH) ₂

As a chemical thermal storage material which can form a hydrate, an inorganic salt, an organic salt, and a hydroxide are mentioned, for example.
Specific examples of the inorganic salt include halides, sulfates, phosphates and silicates. As the halide, for example, fluoride, chloride, bromide, iodide and the like can be mentioned. Specific examples of the fluoride include lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride and calcium fluoride. Specific examples of the chloride include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, iron chloride, zinc chloride, cobalt chloride, nickel chloride, copper chloride, ammonium chloride and the like. It can be mentioned. Specifically as bromide, for example, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, iron bromide, zinc bromide, cobalt bromide, odor And nickel bromide and copper bromide. Specific examples of the iodide include lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, calcium iodide, strontium iodide, barium iodide, iron iodide, zinc iodide, cobalt iodide, Nickel iodide, copper iodide and the like can be mentioned. These may be combined.

Specific examples of the sulfate include lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, yttrium sulfate, lanthanum sulfate, chromium sulfate, manganese sulfate, iron sulfate, cobalt sulfate, sulfuric acid Nickel, copper sulfate, zinc sulfate, cerium sulfate, lead sulfate, aluminum sulfate, aluminum potassium sulfate, ammonium aluminum sulfate and the like can be mentioned. These may be combined.

Specific examples of the phosphate include lithium phosphate, sodium phosphate, calcium phosphate, magnesium phosphate and the like. These may be combined.

Specific examples of the silicic acid include lithium silicate, sodium silicate, potassium silicate, magnesium silicate, calcium silicate and aluminum silicate.

Specific examples of the organic salt include carboxylates, sulfonates, phosphonates, phosphinates and the like. These may be combined.

Carboxylic acid salts are salts of carboxylic acids and metals, and as carboxylic acids, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oleic acid, linoleic acid, linolenic acid, lactic acid, apple Acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, aconitic acid, pyruvic acid, acrylic acid, methacrylic acid Acid, polyacrylic acid, polymethacrylic acid and the like, and specific examples of the metal include lithium, sodium, potassium, magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper, zinc, aluminum and the like It can be mentioned. These may be combined.

The sulfonic acid salt is a salt of sulfonic acid and metal, and specific examples of the sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, taurine, fluorosulfonic acid and the like. Specific examples of the metal include lithium, sodium, potassium, magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper, zinc, aluminum and the like. You may combine these.

The phosphonate is a salt of phosphonic acid and metal, and as the phosphonic acid, specifically, for example, methyl phosphonic acid, ethyl phosphonic acid, propyl phosphonic acid, phenyl phosphonic acid, methylene diphosphonic acid, 1,4-phenylene diphosphonic acid An acid etc. are mentioned. Specific examples of the metal include lithium, sodium, potassium, magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper, zinc, and aluminum. These may be combined.

The phosphinic acid salt is a salt of phosphinic acid and a metal. Specific examples of the phosphinic acid include phenyl phosphinic acid, methyl phosphinic acid, ethyl phosphinic acid, aminoethyl phosphinic acid and the like. For example, lithium, sodium, potassium, magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper, zinc, aluminum and the like can be mentioned. These may be combined.

Examples of the hydroxide include lithium hydroxide, strontium hydroxide and barium hydroxide. These may be combined.

For example, magnesium oxide, calcium oxide, zinc oxide, nickel oxide, cobalt oxide, iron oxide, copper oxide, copper oxide, strontium oxide, barium oxide are converted to oxides by dehydration reaction and to hydroxides by hydration reaction. And lanthanum oxide. These may be combined.

Examples of a chemical heat storage material capable of adsorbing and desorbing water molecules include zeolite, clay, silica gel, porous carbon, an organic structure, and acrylic fine particles. These may be combined.

<Description of chemical heat storage complex>
The chemical heat storage composite according to the present invention has substantially no void derived from other than the chemical heat storage material and the elastomer, which is not substantially hollow (porous), from the viewpoint of obtaining a high heat storage density. Is preferred. Among them, it is desirable that the chemical thermal storage composite has a bulk density equal to or higher than the true density of at least the elastomer alone which does not contain a void, and equal to or lower than the true density when approximately 100% of the chemical thermal storage material is contained. The bulk density of the chemical heat storage composite is desirably 0.9 to 6.0 g / cm ³ . Further, the heat storage density is determined by the type and weight of the heat storage material to be contained, and in actual use, a higher heat storage density is required based on the volume. That is, it is more preferable that the bulk density be 1.0 to 6.0 g / cm ³ , in which the amount of energy does not decrease even when converted to volume. Although a high heat storage density can be obtained by the porosity being almost zero, in the case of unintentionally including air bubbles in the process of curing, the state is not limited. Moreover, when using the additive for the purpose of thermal conductivity improvement etc., it calculates using the weight and volume except these additives.
The bulk density is a density obtained by dividing the weight of a substance by its volume, and the true density is a density excluding connection or an independent void contained in the substance. It is preferable not to include the foaming agent in the chemical heat storage composite and the chemical heat storage composite forming composition, in order to reduce the bulk density of the elastomer having a chemically crosslinked structure.

<Evaluation of bulk density of chemical heat storage composite>
The bulk density of a chemical thermal storage composite is the density obtained by dividing the weight of a substance by its volume as described above, but the value is the true density of the elastomer and the chemical thermal storage medium, and the content thereof It is also possible to calculate from By comparing the measured value with the calculated value, it can be confirmed whether or not there is a void.

<Description of the manufacturing method>
The method of producing the "chemical heat storage composite" of the present invention will be described below.
The chemical heat storage composite is formed, for example, by applying a composition for forming a chemical heat storage composite to a base or the like and heating the base. The heat storage system is more advantageous than the light curing system in the preparation of the composition of the present invention because the chemical heat storage material itself has poor light transmittance due to its content and its content. The composition for forming a chemical heat storage complex is a composition including a chemical heat storage material and a liquid which becomes an elastomer by curing by heating. From the viewpoint of easy handling, those which are liquid at normal temperature are preferably used.

Any liquid which cures to an elastomer upon heating may be used, but preferably it is easy to obtain and more easily processable or durable (heat resistance, light resistance, chemical resistance, etc.), bulky. From the viewpoint of density and high performance in forming a chemical thermal storage composite, a two-component curable composition which is a silicone resin, a polyester resin, an epoxy resin, or a urethane resin is preferable. As described above, the chemical thermal storage composite obtained from such a suitable composition, from the chemical thermal storage composite, is repeatedly used for the endothermic reaction and the exothermic reaction when installed in the heat exchanger even in actual use. Of the chemical heat storage material can be suppressed for a longer period of time.
Examples of the liquid that cures to an elastomer upon heating include a combination of a main agent and a crosslinking agent or catalyst, and preferably, for example, a polymerizable double bond-containing polysiloxane and a double bond polymerization catalyst Moisture-curable terminal isocyanate group urethane prepolymers, epoxy compounds, and the like, combinations of high molecular weight polyols such as polyester polyols and polyether polyols, and polyisocyanates, repeating units of ether structure and / or ester structure, A two-part curable composition such as a combination with a compound selected from the group consisting of an amine compound, a phenol compound and an acid anhydride can be mentioned.
A one-component curable composition such as a solvent solution of polyamic acid which produces a polyimide resin upon heat crosslinking does not exhibit elastomeric properties due to too high an elastic modulus due to curing crosslinking, so any heat storage performance becomes insufficient. .
A crosslinking agent, a catalyst, etc. necessary for curing may be included in advance in the composition for forming a chemical heat storage composite, or may be added to the composition for forming a chemical heat storage composite at the coating step. . When preparing a two-component curable composition, it is preferable to add a crosslinking agent, a catalyst and the like at the stage of coating in view of workability and storage stability.

Examples of the crosslinking agent and the catalyst include sulfur, a crosslinking agent having an amine group, a catalyst, a crosslinking agent having an isocyanate group, and the like, which can be appropriately selected depending on the main component.

Examples of the crosslinking agent or catalyst having an amine group include aliphatic polyamines, alicyclic polyamines, Mannich bases, amine-epoxy adducts, polyamide polyamines, liquid aromatic polyamines and the like.

As a crosslinking agent having an isocyanate group, for example, tolylene diisocyanate (TDI) such as 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4, Diphenylmethane diisocyanate (MDI) such as 4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, Xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, polymer Aromatic polyisocyanates such as diphenylmethane diisocyanate, aliphatic diisocyanates such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), etc. Is raised.

As a catalyst which promotes hardening crosslinking, a platinum catalyst etc. are mentioned, for example. Examples of platinum catalysts include simple platinum, platinum chloride, chloroplatinic acid, chloroplatinic acid salt, platinum chloride, chloroplatinic acid or a complex of chloroplatinic acid salt and a vinyl group-containing siloxane.

The content ratio of the chemically cross-linked elastomer, which is an essential component of the chemical heat storage composite, to the chemical heat storage material may be an optimum ratio according to the raw materials used, and is particularly limited. However, when based on the non-volatile content in the liquid component that is cured by heating to produce an elastomer, which is a raw material, the non-volatile content in the liquid component that cures by heating to produce an elastomer / chemical heat storage material is For example, 5/95 to 50/50, in particular 10/90 to 35/65, in mass conversion, appropriate gas permeation can be performed even if there is a volume change of the chemical thermal storage composite due to repeated heat storage and radiation. It is preferable because high heat storage density can be maintained, and deterioration of the chemical heat storage composite due to stress relaxation is small, and can be made more excellent in durability.

A solvent can also be added to the composition for forming a chemical heat storage complex, if necessary. As the solvent, at least one of an organic solvent and water can be used. Examples of the organic solvent include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate and butyl cellosolve, and alcohols such as methanol and ethanol. It is preferable not to use the organic solvent or to keep the amount as small as possible even if it is used, in order to eliminate the recovery step and to improve the handleability.

A thermally conductive filler can be added to the composition for forming a chemical heat storage composite in order to improve the thermal conductivity. As a heat conductive filler, graphite, silicon carbide, aluminum oxide, magnesium oxide, boron nitride etc. are mentioned, for example. These may be used alone or in appropriate combination of two or more.

An additive for improving the adhesion to the substrate can be added to the composition for forming a chemical heat storage complex.

A rheology control agent or the like for improving the coatability can be added to the composition for forming a chemical heat storage complex.

In order to enhance the dispersion stability of the chemical heat storage material, a dispersant may be included in the composition for forming a chemical heat storage complex.

The preparation method of the composition for forming a chemical heat storage complex is not particularly limited, and a known method can be used. For example, in addition to a chemical heat storage material and a liquid that cures by heating to form an elastomer having a chemically crosslinked structure, the optional component may be a kneader (eg, single screw extruder, twin screw extruder, planetary mixer, twin screw, etc. It can prepare by knead | mixing using a mixer, a high shear type | mold mixer etc.).
In the composition for forming a chemical heat storage composite, the chemical heat storage composite obtained after curing and crosslinking has a high heat storage density as high as possible, and the repeated durability of heat storage and heat radiation over a long period of time incorporated into a heat exchanger increases. Similarly, it is preferable to perform degassing so as to be substantially free of voids derived from other than the chemical heat storage material and the elastomer (ie, to be dense).

<Description of application>
Such a "chemical heat storage composite" of the present invention forms a chemical heat storage material on the surface of a base of a heat exchanger or the like, and can be used in applications such as a chemical heat pump.

<Description of chemical heat storage complex formation process>
The chemical thermal storage composite of the present invention, for example, applies the above-described composition for forming a chemical thermal storage composite to the surface of a substrate, and heats the substrate on which the composition for forming a chemical thermal storage composite is applied. It can form by passing through and. Specifically, it includes a coating step described as follows and a heating step.

<Coating process>
In the application step, the above-mentioned composition for forming a chemical heat storage complex is applied to a substrate. The composition for forming a chemical heat storage complex is preferably a liquid which does not contain a solvent and which is a normal temperature liquid because it is rich in fluidity and it is easy to apply, but if the viscosity is high at ordinary temperature without a solvent, heating etc. It is also possible to apply after improving fluidity. It is preferable that the composition for forming a chemical thermal storage composite containing a solvent is subjected to drying such as solvent removal by a known method simultaneously with or after the application.
Any method may be used as long as the composition for forming a chemical heat storage complex is applied to the substrate, for example, a method of applying by dipping the substrate in the composition for forming a chemical heat storage complex by showering or dipping. And the application method by an applicator etc. are mentioned. Although the base material which apply | coats the composition for chemical thermal storage composite formation is not specifically limited, For example, aluminum which is a metal material used for the heat exchange surface of a heat exchanger, copper, steel materials, stainless steel etc. are mentioned.

<Heating process>
In the heating step, the composition for a chemical heat storage composite on the surface of the substrate is heated after the application step. The composition for a chemical thermal storage composite is heated in the heating step, so that crosslinking proceeds by curing to become an elastomer having a chemical crosslinked structure, and forms a chemical thermal storage composite also including a chemical thermal storage material. Although a heating process can be performed by an electric furnace, a heating oven, etc., it does not specifically limit about the apparatus to heat. The conditions for heat curing may be selected according to the composition of the composition for forming a chemical thermal storage complex to be used. For example, the heating temperature is in the range of room temperature to 300 ° C., and the heating time is 3 minutes to 3 hours In the range of
Although this heating process can also be performed under an atmosphere of oxygen gas or air, for example, when it is performed under an inert gas atmosphere such as nitrogen gas or helium gas, curing inhibition due to heating is less likely to occur. The resulting chemical heat storage composite has high heat storage density and high durability of repeated heat storage and heat radiation over a long period of time when it is incorporated in a heat exchanger.

Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following production examples. The reference example shows a method of preparing a resin for determining the elastic modulus of the resin contained in the chemical heat storage composite.

Reference Example 1
Weigh 1 g of SYLGARD 184 Silicone Elastomer (made by Toray Dow Corning Co., Ltd.) and 0.1 g of SYLGARD 184 Curing Agent (made by Toray Dow Corning Co., Ltd.) in a vial, and use Awatori Neritaro (made by Shinky Co., Ltd.) Stir and degas to obtain a liquid. The obtained liquid was coated on a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, and the coated plate was heated in a nitrogen atmosphere at 200 ° C. for 1 hour to obtain a film of a crosslinked silicone resin elastomer. .

Production Example 1 (Chemical thermal storage composite of crosslinked silicone resin elastomer)
1 g of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of SYLGARD 184 Silicone Elastomer (manufactured by Toray Dow Corning), 0.1 g of SYLGARD 184 Curing Agent (manufactured by Toray Dow Corning), and 1 g of toluene The mixture was weighed in a bottle and stirred and defoamed with Awatori Neritaro (manufactured by Shinky Co., Ltd.) to obtain a paste containing a silicone resin and calcium chloride. The obtained paste is applied onto a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, and the coated plate is heated in a nitrogen atmosphere at 200 ° C. for 1 hour to crosslink silicone resin elastomer and chemical heat storage material A membrane (D1) of a chemical heat storage complex comprising

Reference Example 2
Poly (dimethyl siloxane), vinyl end (weight average molecular weight 25,000, manufactured by Sigma Aldrich Co., Ltd.) 10 g, methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy end (number average molecular weight 950, manufactured by Sigma Aldrich Co.) 0 .5 g, 150 μg of platinum (0) -1,3-divinyl tetramethyldisiloxane complex (manufactured by Tokyo Chemical Industry Co., Ltd.) is weighed into a vial, stirred with Awatori Neritaro (manufactured by Shinky Co., Ltd.), and defoamed The liquid was obtained. The obtained liquid was coated on a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, and the coated plate was heated in a nitrogen atmosphere at 100 ° C. for 1 hour to obtain a film of a crosslinked silicone resin elastomer. .

Production Example 2 (Chemical Heat Storage Composite of Silicone Resin Elastomer)
Poly (dimethyl siloxane), vinyl end (weight average molecular weight 25,000, manufactured by Sigma-Aldrich Co., Ltd.) 10 g, methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy end (number average molecular weight 950, manufactured by Sigma Aldrich Co.) 0 .5 g of platinum (0) -1,3-divinyl tetramethyldisiloxane complex (150 μg from Tokyo Kasei Co., Ltd.) and 10 g of calcium chloride (Wako Pure Chemical Industries, Ltd.) are weighed in a vial Stirring and degassing was carried out with Nerichiro (manufactured by Shinky Co., Ltd.) to obtain a liquid. The obtained liquid is coated on a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, and the coated plate is heated in a nitrogen atmosphere at 100 ° C. for 1 hour to crosslink silicone resin elastomer and chemical heat storage material A membrane (D2) of a chemical heat storage complex comprising

Reference Example 3
Measure 5 g of Pandex GW-1340 (manufactured by DIC Corporation) and 0.3 g of Bernock DN-902S (manufactured by DIC Corporation) in a vial, and stir with Awatori Neritaro (manufactured by Shinky Co., Ltd.) to remove it. Bubbled to give a liquid. The obtained liquid was applied onto a stainless (SUS304) plate (7 cm × 3 cm) using an applicator, and the applied plate was heated in air at 80 ° C. for 1 hour to obtain a film of a crosslinked urethane resin elastomer.

Production Example 3 (Chemical Heat Storage Composite of Cross-linked Urethane Resin Elastomer)
Measure 5 g of Pandex GW-1340 (manufactured by DIC Corporation), 0.3 g of Bernock DN-902S (manufactured by DIC Corporation), and 5 g of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in a vial. Stirring and degassing with Tori Neritaro (product of Shinky Co., Ltd.) to obtain a liquid. The obtained liquid is coated on a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, and the coated plate is heated in a nitrogen atmosphere at 80 ° C. for 1 hour to crosslink the urethane resin elastomer and the chemical heat storage material A membrane (D3) of a chemical heat storage complex comprising

Reference Example 4
Measure 4 g of Dick Dry LX-627M (manufactured by DIC Corporation) and 1 g of KW-40 (manufactured by DIC Corporation) in a vial, and stir and degas with Awatori Neritaro (manufactured by Shinky Corporation) I got a liquid. The obtained liquid was coated on a stainless steel (SUS304) plate (7 cm × 3 cm) using an applicator, and the coated plate was heated in air at 50 ° C. for 3 days to obtain a film of a crosslinked polyester resin elastomer.

Production Example 4 (Chemical Heat Storage Composite of Cross-linked Polyester Resin Elastomer)
Weigh 4 g of Dick Dry LX-627M (manufactured by DIC Corporation), 1 g of KW-40 (manufactured by DIC Corporation), and 5 g of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in a vial. The mixture was stirred and degassed with (manufactured by Shinky Co., Ltd.) to obtain a liquid. The obtained liquid is coated on a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, and the coated plate is heated in a nitrogen atmosphere at 50 ° C. for 3 days to crosslink polyester resin elastomer and chemical heat storage material A membrane (D4) of a chemical heat storage complex comprising

Reference Example 5
Measure 2.84 g of EPICLON EXA-4850-150 (manufactured by DIC Corporation) and 0.16 g of triethylenetetramine (manufactured by Tokyo Kasei Corporation) in a vial, and use Awatori Neritaro (manufactured by Shinky Co., Ltd.) Stir and degas to obtain a liquid. The obtained liquid is applied onto a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, and the coated plate is heated in air at 80 ° C. for 3 hours and 150 ° C. for 2 hours to obtain a crosslinked epoxy resin elastomer I got a membrane.

Production Example 5 (Chemical Heat Storage Composite of Cross-Linked Epoxy Resin Elastomer)
2.84 g of EPICLON EXA-4850-150 (manufactured by DIC Corporation), 0.16 g of triethylenetetramine (manufactured by Tokyo Kasei Corporation), 3 g of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.), and 1 g of toluene The mixture was weighed in a bottle and stirred and defoamed with Awatori Neritaro (manufactured by Shinky Co., Ltd.) to obtain a liquid. The obtained liquid is coated on a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, and the coated plate is heated at 80 ° C. for 3 hours and 150 ° C. for 2 hours in a nitrogen atmosphere to crosslink epoxy resin elastomer A film (D5) of a chemical heat storage composite including the above and a chemical heat storage material was obtained.

Comparative Reference Example 1
Apply 1 g of U-varnish-A (Ube Industries, Ltd.) on a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator, heat the coated plate in air at 200 ° C for 3 hours, A film of resin was obtained.

Comparative Production Example 1 (Chemical Heat Storage Composite of Polyimide Resin)
Apply 2 g of U-varnish-A (manufactured by Ube Industries, Ltd.) and 0.1 g of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) on a stainless steel (SUS 304) plate (7 cm × 3 cm) using an applicator. The coated plate was heated in a nitrogen atmosphere at 200 ° C. for 3 hours to obtain a film (C1) of a chemical heat storage composite containing a polyimide resin and a chemical heat storage material.

[Measurement of glass transition temperature]
The glass transition temperatures of the films obtained in Production Examples 1, 2, 3, 4, 5 and Comparative Production Example 1 were measured. The measurement of glass transition temperature used RSA III made from TA Instruments Co., Ltd. product. The sample was cut into strips of width 0.5 cm and length 4 cm, and the thickness was measured using a micrometer (PMU150-25MX manufactured by Mitutoyo Corp.). This was used as a test piece for measurement. The test piece was attached to a jig for tensile test, and measurement was performed under the conditions of a temperature of −50 to 100 ° C. and a frequency of 1 Hz. If there is a glass transition temperature on the lower temperature side than this condition, re-measure under the same conditions in the range of -140 to 0 ° C, if there is a glass transition temperature on the higher temperature side, the range of 50 ° C to 300 ° C In the same conditions. The temperature at the maximum value of loss tangent (tan δ) obtained by the measurement was taken as the glass transition temperature.

[Measurement of elastic modulus]
The elastic modulus was measured for the films obtained in Reference Examples 1, 2, 3, 4, 5 and Comparative Reference Example 1. The measurement of elastic modulus used RSA III made from TA Instruments Co., Ltd. product. The sample was cut into strips of width 0.5 cm and length 4 cm, and the thickness was measured using a micrometer (PMU150-25MX manufactured by Mitutoyo Corp.). This was used as a test piece for measurement. The test piece was attached to a jig for tensile test, and measurement was carried out under conditions of a temperature of 30 ° C. and a frequency of 1 Hz. The storage elastic modulus (E ') obtained at that time was taken as the elastic modulus. The results are shown in Table 1.

[Measurement of bulk density]
The bulk density of the films obtained in Reference Examples 1, 2, 3, 4, 5 and Comparative Reference Example 1 was measured. The bulk density was determined by the bulk volume and weight of the test piece. The external dimensions of the chemical thermal storage composite, approximately 20 mm long x 20 mm wide, which has been left for at least 1 hour in an environment with a temperature of 23 ° C and a dew point of -15 ° C or less, are measured with calipers with a precision of 0.1 mm. The volume was measured with an accuracy of 0.001 mm using PMU150-25MX manufactured by Mitutoyo Corporation. Then, the weight (g) of the test piece was precisely weighed. The weight of the test piece determined as described above was divided by the bulk volume of the test piece and converted to a unit. Five test pieces were prepared, and among the obtained bulk densities, the average value of the three results excluding the highest one and the lowest one is shown in Table 1 as an actual measurement value.

[Evaluation of heat storage performance]
About 10 mg of the film of the chemical heat storage composite obtained in Production Examples 1, 2, 3, 4, 5 and Comparative Production Example 1 is cut out from a SUS 304 plate, and TG-DTA measurement is performed using this (TG-DTA 2020SA Bruker AX The heat storage performance of the chemical heat storage complex was evaluated by S. Co., Ltd.).

In the evaluation, the temperature was raised to 200 ° C. at 10 ° C./min while flowing nitrogen gas (200 ml / min), held at 200 ° C. for 30 minutes, and subsequently cooled to 80 ° C. at 10 ° C./min. The temperature was maintained at 80 ° C. for 10 minutes, and then the pressure was switched to a nitrogen mixed gas (200 ml / min) with a water vapor partial pressure of 5.6 kPa while maintaining the temperature, and a mixed gas containing water vapor was circulated for 30 minutes. The calorific value was evaluated from the DTA area during adsorption of water vapor for 30 minutes, and this was used as an index of evaluation of heat storage performance. The calorific value was calculated by correcting the obtained DTA area with the heat of fusion of In, Sn, Pb, and the calorific value per 1 kg of the chemical heat storage material was calculated. If the calorific value at this time is 100 kJ / kg or more, it is judged that the heat storage performance of the chemical heat storage composite is present, and if it is less than 100 kJ / kg, it is judged that the heat storage performance of the chemical heat storage composite is not present. The results are shown in Table 1.

As is apparent from Table 1, the heat storage composites including the elastomer having the chemically cross-linked structure in Preparation Examples 1 to 5 have the heat storage compared with Comparative Preparation Example 1 including the polyimide resin having no elastomer property. It is shown that the performance is high, and it means that the chemical heat storage composite comprising the chemical crosslinkable elastomer and the chemical heat storage material shown in Production Examples 1 to 5 can be suitably used as a heat storage material.

All of the chemical thermal storage composites of the above-described examples are manufactured using a composition having more excellent processability, so it is easy without requiring a special time-consuming process before crosslinking. In addition, it is a chemical thermal storage composite that combines durability (heat resistance, light resistance, chemical resistance, etc.), gas permeability and productivity. In addition, also in actual use, when installed in the heat exchanger, in the repetition of the endothermic reaction and the exothermic reaction, the detachment of the chemical thermal storage medium from the chemical thermal storage complex could be suppressed for a longer period of time.

Since the chemical thermal storage composite of the present invention is a chemical thermal storage composite containing an elastomer having a chemical crosslink structure and a chemical thermal storage material, the absorption of the reaction medium gas to the chemical thermal storage material in the matrix resin is It is possible to greatly relieve the stress due to the volume change associated with desorption, and it is difficult for voids to be generated in the composite described above, and the repeated durability of heat storage and heat radiation is excellent while maintaining high heat storage density. When used in combination with a heat exchanger, such a chemical heat storage composite according to the present invention can be used as a waste heat utilization system for a factory, a waste heat utilization system for a vehicle, or a heat utilization system for a house (for example, an air conditioning system) Can be suitably used.

Claims

What is claimed is: 1. A chemical heat storage composite comprising: a chemical heat storage composite containing an elastomer having a chemical crosslink structure and a chemical heat storage material.
A chemical heat storage composite characterized in that it is a chemical heat storage composite having a bulk density of 0.9 to 6.0 g / cm 3 , containing an elastomer having a chemical crosslink structure and a chemical heat storage material.
The chemistry according to claim 1 or 2, wherein the elastomer is at least one selected from the group consisting of natural rubber, diene rubber, olefin rubber, silicone resin, polyester resin, epoxy resin and urethane resin. Heat storage complex.
A composition for forming a chemical thermal storage composite, comprising a liquid that is cured by heating and a chemical heat storage material, wherein the liquid that is cured by the heating becomes an elastomer when it is cured. Composition for chemical thermal storage complex formation.
A composition for forming a chemical thermal storage composite, comprising a liquid that cures by heating, and a chemical heat storage material, wherein the liquid that cures by heating becomes an elastomer when cured, and after curing A composition for forming a chemical heat storage composite, which is prepared so that the chemical heat storage composite has a bulk density of 0.9 to 6.0 g / cm 3 .
The composition for forming a chemical heat storage composite according to claim 4, further comprising a solvent.
7. The at least one resin selected from the group consisting of natural rubber, diene rubber, olefin rubber, silicone resin, polyester resin, epoxy resin and urethane resin. The composition for forming a chemical heat storage complex according to any one of the preceding claims.
A process for applying the composition for forming a chemical heat storage complex according to any one of claims 4 to 7 on the surface of a substrate, and heating the substrate on which the composition for forming a chemical heat storage complex is applied And a process of forming a chemical thermal storage composite.