KR20200078178A - Composition comprising phase change material and method for producing thereof - Google Patents

Abstract

The present invention relates to a composition comprising a monoester compound or a diester compound as a phase change material (PCM), and to a method for producing the phase change material. The method for producing the phase change material according to the present invention has a higher yield and simpler removal of byproducts compared to conventional methods.

Description

Composition comprising phase change material and manufacturing method therefor {Composition comprising phase change material and method for producing thereof}

The present invention relates to a composition comprising a phase change material and a method for manufacturing the same.

A phase change material (PCM) is a material capable of maintaining a constant temperature around the PCM or storing energy by using the absorption or release characteristics of latent heat of the material by causing a phase change when the ambient temperature changes. Therefore, PCM is used as a latent heat storage material, heat storage material, heat storage material, heat regulating material, building materials that require temperature maintenance or energy storage, heating and cooling fields in buildings or special-purpose spaces including building panels, automobiles, aerospace, High-tech weapons, heat sinks for electronic, instrumentation, and communication equipment (TEM), nuclear fusion reactor cooling, storage and transportation of biological and biochemical materials, and high-tech industries such as medical treatment, heat pumps, heat pipes, and heat recovery It is used in food industry fields such as production, storage and distribution of agricultural products, marine products, or livestock products, as well as in the living industries such as systems, cold storage (low temperature PCM cold storage refrigeration and freezing) systems, leisure ships, fisheries, kitchenware, and special clothing. .

Traditionally, phase change materials can be divided into inorganic, organic and eutectic PCM, inorganic PCM is divided into salt hydrate, and metal, and organic PCM is divided into paraffin compound and fatty acid, Eutectic PCM is divided into organic-organic, inorganic-inorganic and organic-inorganic. Inorganic PCM is, for example, KF·4H ₂ O, Mn(NO ₃ )2·6H ₂ O, CaCl ₂ ·6H ₂ O, LiNO ₃ ·3H ₂ O, and Na ₂ SO ₄ ·10H ₂ O Most of the hydrate-based materials. Inorganic PCM exhibits high latent heat per unit volume, but has the disadvantage of being affected by phase change properties due to corrosion or supercooling. The eutectic mixture is, for example, CaCl ₂ ·6H ₂ O + MgCl ₂ ·6H ₂ O, CaCl ₂ + NaCl + KCl + H ₂ O, Ca(NO ₃ ) ₂ ·4H ₂ O + Mg(NO ₃ ) ₂ · Means a mixture of two or more components that melt at the lowest temperature, such as 6H ₂ O, and Na(CH ₃ COO)·3H ₂ O + CO(NH ₂ ) ₂ . On the other hand, the organic PCM is generally low in density, has a small corrosive property and a small volume expansion compared to an inorganic phase change material, for example, butyl stearate, paraffin, capric-lauric acid, dimethyl sabacate, Materials such as polyglycol E600, 1-dodecanol. However, organic PCM has the disadvantages of low latent heat, density and low thermal conductivity.

Accordingly, it is necessary to develop an organic PCM material capable of controlling the phase transition temperature while having high latent heat and a method for manufacturing the same.

International Patent Publication No. WO2006/062610 U.S. Patent No. 665771

An object of the present invention is to provide an environmentally friendly phase change material and a method for manufacturing the same.

1. A composition for temperature control comprising a compound represented by Formula 1 or a compound represented by Formula 2 or both as a phase change material:

[Formula 1]

(In the above formula 1

R ₁ is a straight-chain or ground type C _m H _2m+1 -,

R ₂ is C _n H _2n+1 (O(CH ₂ ) ₂ ) _p -,

m is an integer from 5 to 20,

n is an integer from 1 to 5,

p is an integer from 0 to 3.)

[Formula 2]

(In the formula 2 above

R1 is a straight chain or pulverized C _q H _2q+1 -,

R ₂ is -((CH ₂ ) ₂ O) _r (CH ₂ ) ₂ -,

q is an integer from 5 to 15,

r is an integer from 0 to 14.).

2. The composition of item 1, wherein p and r are each non-zero.

3. The composition of item 1 or 2, wherein the phase transition temperature is -20°C to 70°C.

4. In item 1 or 2, in formula 1, R ₁ is C ₁₅ H ₃₁ -and R ₂ is CH ₃ OC ₂ H ₄ -; In Formula 1, R ₁ is C ₁₇ H ₃₅ -and R ₂ is CH ₃ (OC ₂ H ₄ ) ₂ -; In Formula 1, R ₁ is C ₁₇ H ₃₅ -and R ₂ is CH ₃ (OC ₂ H ₄ ) ₃ -; In Formula 1, R ₁ is C ₁₅ H ₃₁ -and R ₂ is C ₂ H ₅ OC ₂ H ₄ -; In Formula 1, R ₁ is C ₁₇ H ₃₅ -and R ₂ is C ₂ H ₅ (OC ₂ H ₄ ) ₂ -; In Formula 1, R ₁ is C ₁₁ H ₂₃ -and R ₂ is C ₁₂ H ₂₄ -; In Formula 1, R ₁ is C ₁₇ H ₃₅ -and R ₂ is C ₆ H ₁₂ -; In Formula 2, R ₁ is C ₉ H ₁₉ -and R ₂ is -C ₂ H ₄ OC ₂ H ₄ -; In Formula 2, R ₁ is C ₉ H ₁₉ -and R ₂ is -C ₂ H ₄ (OC ₂ H ₄ ) ₂ -; In Formula 2, R ₁ is C ₁₁ H ₂₃ -and R ₂ is an oxaalkylene radical derived from PEG 200; R ₁ in Formula 2 is C ₁₁ H ₂₃ -and R ₂ is an oxaalkylene radical derived from PEG 400; And in Formula 2, R ₁ is C ₉ H ₁₉ -and R ₂ is at least one compound selected from oxaalkylene radicals derived from PEG 600.

5. R ₁ COOCH ₃ and R ₂ -OH with dibutyltin oxide (DBTO) as the catalyst; Or R ₁ COOCH ₃ , and HO-R ₂ -OH, comprising the steps of reacting, to prepare a compound represented by Formula 1 or a compound represented by Formula 2:

[Formula 1]

(In the above formula 1

R ₁ is a straight-chain or ground type C _m H _2m+1 -,

R ₂ is C _n H _2n+1 (O(CH ₂ ) ₂ ) _p -,

m is an integer from 5 to 20,

n is an integer from 1 to 5,

p is an integer from 0 to 3.)

[Formula 2]

(In the formula 2 above

R1 is a straight chain or pulverized C _q H _2q+1 -,

R ₂ is -((CH ₂ ) ₂ O) _r (CH ₂ ) ₂ -,

q is an integer from 5 to 15,

r is an integer from 0 to 14.).

6. The method according to item 5, wherein R ₁ COOCH ₃ :R ₂ -OH or R ₁ COOCH ₃ :HO-R ₂ -OH is 1:5 (mol:mol).

7. The method according to item 5 or 6, wherein the reaction is carried out at 100 mbar to 500 mbar.

8. The method according to item 5 or 6, wherein the reaction is performed at 130°C to 150°C.

9. The method of item 5, wherein p and r are each non-zero.

10. A product comprising the composition of item 1 or 2.

Since the phase change material prepared according to the present invention has a high latent heat with various phase change temperatures, it can be used in building interior materials, functional clothing, bedding, automotive interior materials, heat protection systems for digital equipment and electric heating devices, or medical tools.

In addition, the method for manufacturing a phase change material according to the present invention can produce a phase change material with a higher yield and/or conversion rate than the conventional method, and shorten the reaction time.

1 to 38 show ¹ H NMR data of each compound.

The present invention will now be more fully described below with reference to the accompanying drawings, but only some, but not all, embodiments of the invention are illustrated. Indeed, these inventions may be embodied in many different forms and should not be construed as limited to the embodiments presented herein. The singular form used in this specification and the appended claims includes a plurality of objects unless expressly indicated otherwise.

The term “phase change material” (PCM) of the present invention can be used interchangeably with “phase change material” and stores a large amount of energy according to the state change of a material such as melting or solidifying at a specific temperature. And a material capable of releasing, and the term “latent heat” of the present invention means heat absorbed or released without a change in temperature during a phase change.

The term “DSC (differential scanning calorimeter)” of the present invention includes a furnace for a sample and a furnace for a reference having independently a sensor made of a heater and a platinum resistor, and the temperature of the sample. It is a device that shows the heat supplied as a function of temperature or time so that when there is a change, it is equal to the temperature of the standard.

The term “temperature control” of the present invention refers to a property that does not react sensitively to changes in ambient temperature or external temperature and is maintained at a substantially constant temperature. Since the composition for temperature control according to the present invention has a high latent heat storage ability, when the ambient temperature is high, a phase transition occurs from a solid to a liquid, and by absorbing a lot of heat, the internal temperature can be maintained substantially constant, and the ambient temperature When is lowered, a phase transition occurs from a liquid to a solid, and in the meantime, the internal temperature can be maintained substantially constant by releasing a lot of heat.

The term “phase transition temperature” of the present invention means a temperature at which a phase change occurs.

The phase change material of the present invention is a building material, a building or a special purpose space containing building panels, air conditioning, automobile, aerospace, high-tech weapons, heat sinks of electronic, measuring and communication devices (TEM), nuclear fusion cooling, biological or biochemical State-of-the-art industrial fields such as storage, transportation and physical therapy medical equipment, heat pumps, heat pipes, heat recovery systems, cold storage (low temperature PCM cold storage and refrigeration) systems, leisure vessels, fisheries, kitchenware, It can be used in the field of living industry, such as special clothing, and in the food industry, such as production, storage, and distribution of agricultural products, marine products, or livestock products.

As used herein, the terms “about”, “substantially”, and the like are used in or near the numerical values when manufacturing and material tolerances unique to the stated meanings are presented, to aid in understanding the present invention. Accurate or absolute figures are used to prevent unscrupulous use of the disclosed disclosure by unscrupulous intruders.

In one embodiment of the present invention, there is provided a composition for temperature control comprising a compound represented by Formula 1 or a compound represented by Formula 2 or both as a phase change material.

[Formula 1]

(In the formula 1, R ₁ is a straight or pulverized C _m H _{2m + 1} -, R ₂ is C _n H _{2n + 1} (O((CH ₂ ) ₂ ) _p -, m is 5 to 20 Integer, n is an integer from 1 to 5, p is an integer from 0 to 3, preferably p is an integer other than 0.)

For example, CH ₃ (CH ₂ ) ₁₄ COOCH ₃ , CH ₃ (CH ₂ ) ₁₄ COOC ₂ H ₄ OCH ₃ , CH ₃ (CH ₂ ) ₁₄ COO(C ₂ H ₄ O) ₂ CH ₃ , and CH ₃ (CH ₂ ) ₁₄ COO(C ₂ H ₄ O) ₃ The phase transition temperatures of CH ₃ are 29.91℃, 25.69℃, 20.5℃ and 22.62℃, respectively, but the latent heat of each is 200 J/g, 185.1 J/g, 194.5 J /g, and 161.4 J/g. As described above, when the R ₂ includes an ether bond, the phase transition temperature can be controlled within a range that does not significantly damage latent heat depending on the number of ether bonds.

[Formula 2]

In Chemical Formula 2, R1 is a straight-chain or pulverized C _q H _2q+1 -, R ₂ is -((CH ₂ ) ₂ O) _r (CH ₂ ) ₂ -, q is an integer of 5 to 15, r is an integer from 0 to 14. The oxaalkylene radical (-((CH ₂ ) ₂ O) _r (CH ₂ ) ₂ -) may be derived from PEG 200, PEG 400, or PEG 600. In one embodiment of the invention, r is preferably an integer other than zero.

Paraffin-based compounds are known as conventional phase-transition materials, but the phase-transfer materials of the present invention are fatty acid-based ester compounds, which are more environmentally friendly than paraffin-based compounds and may exhibit a temperature control effect equal to or higher than that of paraffin-based compounds.

In one embodiment of the present invention, the phase change material may be selected based on the phase change temperature according to the application field. For example, but not limited to, when the phase change material is used as a building material, the phase transition temperature is preferably 24 ℃ to 30 ℃, 24 ℃ to 27 ℃ or 27 ℃ to 30 ℃.

In one embodiment of the present invention, the compound represented by Formula 1 or 2 is dodecanoic acid, methyl dodecanoate, ethyl dodecanoate, butyl dodecanoate, 2-methoxyethyl dodecanoate, 2-ethoxyethyl dode Canoate, 2-butoxyethyl dodecanoate, 2-(2-methoxyethoxy)ethyl dodecanoate, 2-(2-ethoxyethoxy)ethyl dodecanoate, 2-(2-butoxye Ethoxy)ethyl dodecanoate, 2-(2-(2-methoxyethoxy)ethoxy)ethyl dodecanoate, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl dodecanoate, tetra Decanoic acid, methyl tetradecanoate, ethyl tetradecanoate, butyl tetradecanoate, 2-methoxyethyl tetradecanoate, 2-ethoxyethyl tetradecanoate, 2-butoxyethyl tetradecanoate , 2-(2-methoxyethoxy)ethyl tetradecanoate, 2-(2-ethoxyethoxy)ethyl tetradecanoate, 2-(2-butoxyethoxy)ethyl tetradecanoate, 2 -(2-(2-methoxyethoxy)ethoxy)ethyl tetradecanoate, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl tetradecanoate, hexadecanoic acid, methyl hexade Canoate, ethyl hexadecanoate, butyl hexadecanoate, 2-methoxyethyl hexadecanoate, 2-ethoxyethyl hexadecanoate, 2-butoxyethyl hexadecanoate, 2-(2- Methoxyethoxy)ethyl hexadecanoate, 2-(2-ethoxyethoxy)ethyl hexadecanoate, 2-(2-butoxyethoxy)ethyl hexadecanoate, 2-(2-(2 -Methoxyethoxy)ethoxy)ethyl hexadecanoate, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl hexadecanoate, octadecanoic acid, methyl octadecanoate, ethyl octade Canoate, butyl octadecanoate, 2-methoxyethyl octadecanoate, 2-ethoxyethyl octadecanoate, 2-butoxyethyl octadecanoate, 2-(2-methoxyethoxy)ethyl Octadecanoate, 2-(2-ethoxyethoxy)ethyl octadecanoate, 2-(2-butoxyethoxy)ethyl octadecanoate, 2-(2-(2-methoxyethoxy) Ethoxy)ethyl octadecanoate, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl octadecanoate, dodecyl dodeca Noate, tetradecyl tetradecanoate, hexadecyl hexadecanoate, hexyl octadecanoate, octyl octadecanoate, or decyl octadecanoate, but is not limited thereto.

The composition according to the invention may further comprise a flame retardant, or a bulking agent. The flame retardant may be, but is not limited to, halogenated flame retardants containing chlorine or bromine atoms, phosphorus flame retardants, nitrogen flame retardants, inorganic flame retardants, halogen-nitrogen flame retardants, and halogen-phosphorus flame retardants.

Tetrabromocyclooctane, dibromoethyldibromocyclohexane, hexabromocyclododecane, 1,2,5,6,9,10-hexabromocyclododecane, tetrabromobutane as the halogenated flame retardant , Tribromodiphenyl ether, tetrabromodiphenyl ether, pentabromoethylbenzene, pentabromotoluene, pentabromodiphenyl ether, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, decabrobro Modiphenyl ethane, bis(tribromophenoxy)ethane, bis(tribromophenoxy)ethane, decabromobiphenyl, 1,3-bis(pentabromophenoxy)propane, 1,6-bis(pentabro Mofenoxy) hexane, pentabromo (tetrabromophenoxy) benzene, tetradecabromodiphenoxy benzene, 1,2,4,5-tetrabromo-3,6-bis[(pentabromophenoxy City)methyl]benzene, bis(pentabromobenzyl) tetrabromoterephthalate, pentakis(bromomethyl)benzene, bis(2,4,6-tribromophenyl) carbonate, tetrabromobisphenol A bis(2 ,3-dibromopropyl)oxide, tetrabromobisphenol A dimethyl ether, tetrabromophthalic anhydride, tribromophenyl maleimide, ethylene bis (tetrabromophthalimide), tetrabromophthalimide, ethylene bis (Dibromonobonaneindicacarboximide), tetrabromobisphenol S bis (2,3-dibromopropyl ether), disodium tetrabromophthalate, chlorinated paraffin and tetrabromobisphenol A-based carbonate and epoxy oligomer, preliminary At least one of polymer and copolymer derivatives is included. Examples of the tetrabromobisphenol A-based polymer include epichlorohydrin-tetrabromobisphenol A-2,4,6-tribromophenol copolymer, tetrabromobisphenol A-oxirane polymer, 1-chloro-2, 3-epoxypropane and polymethylenepolyphenylene polyisocyanate with tetrabromobisphenol A oligomer reaction product, ethylene dibromide-tetrabromobisphenol A copolymer, bisphenol A-bisphenol A diglycidyl ether-tetra Bromobisphenol A copolymer, bisphenol A diglycidyl ether-tetrabromobisphenol A copolymer, tetrabromobisphenol A-bisphenol A-phosgene polymer, tetrabromobisphenol A carbonate oligomer and polymer, tetrabromobisphenol A And dicarbonate polymers with phenol, dibromobisphenols with tetrabromobisphenol A and bis(2,4,6-tribromophenyl), and condensates to tetrabs of 2,4,6-tribromophenol. Lomobisphenol A-4,4'-isopropylidene diphenol-phosgene may be used, but is not limited thereto.

The phosphorus flame retardant may include at least one of alkyl and aryl phosphate, phosphonate, phosphinate and phosphine oxide. Examples of the compound include triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, diphenyl xylyl phosphate, 2-biphenylyl diphenyl phosphate, butylated triphenyl phosphate, tert-butyl Phenyl diphenyl phosphate, bis-(tert-butylphenyl)phenyl phosphate, tris(tert-butylphenyl) phosphate, tris(2,4-di-tert-butylphenyl)phosphate, isopropylated triphenyl phosphate, Isopropylated triphenyl phosphate residue, isopropylated tert-butylated triphenylphosphate, tert-butylated triphenyl phosphate, isopropylphenyl diphenyl phosphate, bis(isopropylphenyl) phenylphosphate, 3,4-dia Isopropylphenyl diphenyl phosphate, tris(isopropylphenyl) phosphate, (1-methyl-1-phenylethyl)phenyl diphenyl phosphate, nonylphenyl diphenyl phosphate, 4-[4-hydroxyphenyl (propane-2) ,2-diyl)]phenyl diphenyl phosphate, 4-hydroxyphenyl diphenyl phosphate, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), bis(ditolyl) isopropylidenedi- p-phenylene bis(phosphate), diisodecyl phenyl phosphate, dibutyl phenyl phosphate, methyl diphenyl phosphate, butyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, diphenyl octyl phosphate, isooctyl diphenyl phosphate, Diphenyl isodecyl phosphate, isopropyl diphenyl phosphate, diphenyl lauryl phosphate, tetradecyl diphenyl phosphate, cetyl diphenyl phosphate, cresic dicarboxylic acid diphenyl phosphate, diphenyl 2-(methacryloyloxy)ethyl phosphate , Triethyl phosphate, tri(butoxyethyl)phosphate, 3-(dimethylphosphono) propionic acid methyloamide, dimethyl methyl phosphonate, diethyl ethyl phosphonate, dimethyl propyl phosphonate, diethyl [ (Diethane allamino)methyl]phosphonate, bis[(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)meth Tyl] methyl phosphonate, P,P'-dioxide, (5-ethyl-2-methyl-1,3,2-dioxaphospholinan-5-yl)methyl dimethyl phosphonate P-oxide, aluminum Bis(4,4',6,6'-tetra-tert-butyl-2,2'-methylenediphenyl phosphate) hydroxide, bis[p-(1,1,3,3-tetramethylbutyl) Phenyl] hydrogen phosphate, phosphinidylditrimethanol, secondary-butylbis(3-hydroxypropyl)phosphine oxide, tris(3-hydroxypropyl)phosphine oxide, isobutylbis(hydroxypropyl) phosphine Oxide, isobutyl bis(hydroxymethyl) phosphine oxide, triphenylphosphine monooxide, and tris(2,3-epoxypropyl) phosphate may be used, but are not limited thereto.

Melamine cyanurate, 1,3,5-tris(2,3-dibromopropyl) isocyanurate, 1,3,5-triglycidyl isocyanurate, 1,3 as the nitrogen-based compound ,5-tris(2-hydroxyethyl) isocyanurate, tris(2-acryloxyethyl) isocyanurate, 1,3,5-triazine-2,4,6-tri tri-2 ,1-ethanediyl triacrylate, tris(hydroxyethyl) isocyanurate diacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate and tris(2-methacryloyloxy Ethyl) isocyanurate, and the like, but is not limited thereto.

As the inorganic flame retardant, aluminum trihydrate (ATH), magnesium hydroxide (MDH), zinc borate, inorganic phosphorus compounds, for example, ammonium polyphosphate (APP), red phosphorus, etc. may be used, but is not limited thereto. .

Also 2,4,6-tris (2,4,6-tribromophenoxy)-1,3,5-triazine, 1,3,5-tris (2,3-dibromopropoxy)-2, Halogen-nitrogen flame retardants such as 4,6-triazine and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane-cyanuric chloride copolymer, Tris (bromocresyl) Phosphate, tris(4-bromo-3-methylphenyl) phosphate, tris(dibromophenyl) phosphate, tris(2,4,6-tribromophenyl) phosphate, tris(tribromophenyl) phosphate, tris(tribromopentyl ) Halogen-phosphorus flame retardants such as phosphate, tris(2-bromooctyl) phosphate, tris(2-bromoisopropyl) phosphate, and tris(2-bromopropyl) phosphate may be used, but are not limited thereto.

The extender improves the storage stability and increases the viscosity of the composition of the present invention to improve the operability, calcium carbonate, diatomaceous earth, silica, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, One or more selected from the group consisting of modified urethane (urethane modified) may be used, but is not limited thereto.

In one embodiment of the present invention, the composition for temperature control may be included in the product in the form of a capsule. Since the phase change material contained in the composition for temperature control may exist in the form of a solid or liquid phase, encapsulation can prevent the phase change material from flowing out and increase stability. As the capsule coating material, a polymer material such as polyurethane, urea resin, cross-linked nylon, melanin resin, and gelatin, which is hydrophobic, may be used, but is not limited thereto. In addition, in another embodiment of the present invention, the composition for temperature control may be in the form of a structure or filler impregnated with a porous inorganic material.

The composition according to the present invention can use an appropriate surfactant for the dispersion of the phase change material into stable and smooth microparticles. Examples of surfactants that can be used are alkali metal salts or ammonium salts of fatty acids (e.g., alkali metal salts of oleic acid and stearic acid), alkali metal or ammonium alkyl sulfates (e.g. sodium lauryl sulfate, or isostearic acid) Di methylethanolamine salts), fatty alkyl alkoxylates or equivalent sulfates or phosphates (e.g. sodium laureth-4 sulfate), alkylammonium salts, or nonyl (sodium salt of nonoxynol-10 phosphate), Alkali metal salts or ammonium salts of alkyl amphodicarboxylates (e.g., sodium cocoamphodipropionate), or alkali metal or ammonium salts of alkyl, alkylphenoxy or alkyloxinol sulfosuccinates (e.g. Isodiumdeset-6 sulfosuccinate). These surfactants can be used alone, but can be used in combination with other co-surfactants. In addition, the surfactant is selected depending on the temperature at which the process is performed in the dispersion process and the specific application.

In one embodiment of the present invention, a product comprising the composition is provided. The product may be a building material, textiles, automobiles, batteries, computer hardware, carriers, medical supplies, boilers, kitchenware, or agricultural production facilities, but is not limited thereto. Since the compound according to the present invention has high latent heat and can be applied in various temperature ranges, it can be selectively used according to the desired phase transition temperature.

In addition, a method of preparing a compound represented by Formula 1 or a compound represented by Formula 2 in one embodiment of the present invention is provided.

In one embodiment of the production method according to the invention, R ₁ COOCH ₃ , and R ₂ -OH; Or R ₁ COOCH ₃ , and HO-R ₂ -OH, and adding dibutyltin oxide (DBTO).

The conventional method for synthesizing esters is shown in Scheme 1 below.

[Scheme 1]

At this time, the molar ratio of C16:2-ethoxyethanol is 1:2, and toluene is used as the solvent. H ₂ SO ₄ used as a catalyst is added at 1 wt% of C16 used, and the reaction proceeds at 120°C. After the reaction was completed, the solution was dissolved in ethyl acetate, washed with an aqueous sodium carbonate solution, and the organic layer was removed with magnesium sulfate, and then ethyl acetate was removed. The yield of the ester according to the reaction is about 70%.

On the other hand, in the method for preparing a phase change material according to the present invention, dibutyltin oxide (DBTO) is used as a catalyst.

In the manufacturing method according to the present invention, dibutyltin oxide can be recycled.

In one embodiment of the present invention, R ₂ -OH or HO-R ₂ -OH is a reactive solvent, reacting while forming a solution with another reactant, an ester compound, to yield a phase change material of the present invention. Therefore, a separate solvent is not required in this embodiment.

As an embodiment of the present invention, 2-ethoxyethyl hexadecanoate can be obtained by reacting methyl hexadecanoate with 2-ethoxyethanol in the presence of dibutyltin oxide (Scheme 2).

[Scheme 2]

The molar ratio of C16:2-ethoxyethanol in the reaction is 1:1 to 1:8, or 1:2 to 1:7. The solvent is 2-ethoxyethanol, one of the reactants. Dibutylene oxide used as a catalyst is added at 0.1 to 1 wt% of C16 used, and the reaction proceeds at 120°C to 160°C, or at 120°C to 150°C. The reaction proceeds under reduced pressure to 100 mbar to 500 mbar, and methanol produced during the reaction is removed using a distiller. After the reaction is completed, the residual ethoxyethanol is removed under reduced pressure in a vacuum, and the residue is filtered through a silica filter to finally obtain CH ₃ (C ₂ H ₄ ) ₇ COOC ₂ H ₄ OC ₂ H ₄ . The conversion of the reaction is 98% to 99%, and the yield is 97% to 98%. By using the method according to the invention it is possible to increase the production yield and/or conversion, and to significantly shorten the reaction time.

Reaction Scheme 2 above may be generalized and expressed as Reaction Scheme 3 below.

[Scheme 3]

Hereinafter, the present invention will be described with specific examples. However, the present invention should not be interpreted as being limited to the following examples.

Preparation Example 1. Synthesis of monoester PCM

250 g of methyl palmitate (methyl palmitate; or methyl hexadecanoate; C16) was placed in a 1L 2-neck round bottom flask, with a thermometer installed to enable internal temperature measurement and connected to a distillation apparatus. To this, 0.25 g of dibutyltin oxide (DBTO) was added as a catalyst, and 250 g of 2-ethoxyethanol was added (C16: 2-ethoxyethanol=1:2 (mol:mol). )). The flask was heated to 120° C. using an oil bath and decompressed to 500 mbar to react methyl palmitate and 2-ethoxyethanol (Scheme 2).

[Scheme 2]

The methanol generated by the reaction could be separated by a distiller, and the reaction time was measured based on the point at which methanol was distilled. After the reaction was completed, 2-ethoxyethanol was removed by reducing the pressure while maintaining the external temperature, and the resulting solution was passed through a glass filter filled with silica to give 2-ethoxyethyl hexadecano. Eight was purified.

Production Example 2. Under non-decompression conditions Synthesis of monoester PCM

In Reaction Example 1, the reaction was performed in the same manner as in Preparation Example 1, except that the reaction was performed at normal pressure without decompression to 500 mbar.

Production Example 3. According to the conventional method Synthesis of monoester PCM

C16 and 2-ethoxyethanol were added to the toluene solvent in a molar ratio of 1:2. H ₂ SO ₄ used as a catalyst was added at 1 wt% of the used C16, heated to 120° C., and reacted in a reflux process. After the reaction was completed, the solution was vacuum-removed to remove ethoxyethanol, dissolved in ethyl acetate, washed with an aqueous sodium carbonate solution, and then the organic layer was removed with magnesium sulfate to remove ethyl acetate, and then a column was used. Finally, 2-ethoxyethyl hexadecanoate was obtained.

[Scheme 1]

Preparation Example 1 Preparation Example 2 Preparation Example 3 Synthetic process Used molar ratio C16: 2-ethoxyethanol = 1: 2 C16: 2-ethoxyethanol = 1: 2 C16: 2-ethoxyethanol = 1: 2 menstruum 2-ethoxyethanol 2-ethoxyethanol toluene catalyst DBTO DBTO H ₂ SO ₄ Temperature 120℃ 120℃ 120℃ pressure 500 mbar Normal pressure (1013 mbar) Normal pressure (1013 mbar) Refining process Removal of 2-ethoxyethanol under reduced pressure Removal of 2-ethoxyethanol under reduced pressure Removal of 2-ethoxyethanol under reduced pressure
Dissolve in ethyl acetate and wash with aqueous sodium carbonate solution
Remove organic layer with magnesium sulfate
Ethyl acetate removal Reaction time About 5 hours About 27 hours About 30 hours Conversion rate 98-99% 97-98% About 80% yield 97-98% 97-98% 70%

As shown in Table 1, the yield according to Preparation Example 3 was 70%, but the yields of Preparation Examples 1 and 2 were 97-98%, and particularly, the conversion rates of Preparation Examples 1 and 2 were 98-, respectively. 99% and 97-98%. In addition, in the case of Production Example 1, the reaction time was reduced by 80% or more compared to Production Example 2 by proceeding the reaction under reduced pressure at 500 mbar.

Example 1. Synthesis of monoester PCM of various lengths

Hereinafter, PCMs of various lengths were synthesized according to the following Reaction Scheme 3 in the same manner as in Preparation Example 1.

[Scheme 3]

In Reaction Scheme 3, R ₁ COOCH ₃ used ₁ equivalent of methyl dodecanoate, methyl tetradecanoate, methyl hexadecanoate, and methyl octadecanoate, and R ₂ -OH was ethanol, butanol, 2-methoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2- (2-(2-methoxyethoxy)ethoxy)ethanol, 2-(2-(2-ethoxyethoxy)ethoxy)ethanol, dodecanol, tetradecanol, and hexadecanol were used in 3 equivalents. , DBTO was used ₁ wt% of the used R ₁ COOCH ₃ .

Accordingly, dodecanoic acid, methyl dodecanoate, ethyl dodecanoate, butyl dodecanoate, 2-methoxyethyl dodecanoate, 2-ethoxyethyl dodecanoate, 2-butoxyethyl dodecanoate, 2- (2-methoxyethoxy)ethyl dodecanoate, 2-(2-ethoxyethoxy)ethyl dodecanoate, 2-(2-butoxyethoxy)ethyl dodecanoate, 2-(2-(2 -Methoxyethoxy)ethoxy)ethyl dodecanoate, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl dodecanoate, tetradecanoic acid, methyl tetradecanoate, ethyl tetradecanoate , Butyl tetradecanoate, 2-methoxyethyl tetradecanoate, 2-ethoxyethyl tetradecanoate, 2-butoxyethyl tetradecanoate, 2-(2-methoxyethoxy)ethyl tetrade Canoate, 2-(2-ethoxyethoxy)ethyl tetradecanoate, 2-(2-butoxyethoxy)ethyl tetradecanoate, 2-(2-(2-methoxyethoxy)ethoxy )Ethyl tetradecanoate, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl tetradecanoate, hexadecanoic acid, methyl hexadecanoate, ethyl hexadecanoate, butyl hexadecanoate , 2-methoxyethyl hexadecanoate, 2-ethoxyethyl hexadecanoate, 2-butoxyethyl hexadecanoate, 2-(2-methoxyethoxy)ethyl hexadecanoate, 2-( 2-ethoxyethoxy)ethyl hexadecanoate, 2-(2-butoxyethoxy)ethyl hexadecanoate, 2-(2-(2-methoxyethoxy)ethoxy)ethyl hexadecanoate , 2-(2-(2-ethoxyethoxy)ethoxy)ethyl hexadecanoate, octadecanoic acid, methyl octadecanoate, ethyl octadecanoate, butyl octadecanoate, 2-methoxyethyl Octadecanoate, 2-ethoxyethyl octadecanoate, 2-butoxyethyl octadecanoate, 2-(2-methoxyethoxy)ethyl octadecanoate, 2-(2-ethoxyethoxy )Ethyl octadecanoate, 2-(2-butoxyethoxy)ethyl octadecanoate, 2-(2-(2-methoxyethoxy)ethoxy)ethyl octadecanoate, 2-(2- (2-ethoxyethoxy)ethoxy)ethyl octadecanoate, dodecyl dodecanoate, tetradecyl tetradecanoate, hexadecyl hexa Decanoate, hexyl octadecanoate, octyl octadecanoate, and decyl octadecanoate were synthesized.

Example 2. Measurement of phase transition temperature and latent heat of monoester PCM

The phase transition temperature and latent heat of the PCM synthesized according to Example 1 were measured using a differential scanning calorimeter (DSC). At this time, 5 mg of PCM was used, and liquid PCM was weighed by placing a sample in which the solvent was completely removed using an eyedropper in an aluminum pan, and solid PCM was finely ground with a mortar and then put into an aluminum pan using a spettura. After pressing with a spatula to compress each other, the weight was measured, and the phase transition temperature and latent heat were measured according to the following method:

① Keep for 1 minute at the lowest temperature;

② Heating from the lowest temperature to the highest temperature at 5℃/min;

③ maintained at the highest temperature for 1 minute;

④ Cooling at 5℃/min from the highest temperature to the lowest temperature;

⑤ maintained for 1 minute at the lowest temperature;

⑥ heating from lowest temperature to highest temperature at 5℃/min;

⑦ maintained for 1 minute at the highest temperature;

⑧ Cooling at 5℃/min from the highest temperature to the lowest temperature; And

⑨ Keep for 1 minute at the lowest temperature.

The ① to ⑤ cycle 1, and the ⑥ to ⑨ is cycle 2, after measuring a total of two cycles, the phase transition temperature and latent heat value were measured as the second cycle. The lowest and highest temperatures according to R ₁ are shown in Table 2 below.

R ₁ COO- Minimum temperature (℃) Maximum temperature (℃) Dodecanoate -80 20 Tetradecanoate -50 30 Hexadecanoate -10 60 Octadecanoate -10 60

The measured phase transition temperature and latent heat values are shown in Table 3 below.

* In the above table, C12, C14, C16 and C18 represent the number of carbons of R ₁ COO- in the ester among the reactants of Scheme 3.

Production Example 4. Synthesis of diester PCM

To produce diester PCM, ₁ wt% of R ₁ COOCH ₃ used in 4 equivalents of R ₁ COOCH ₃ and 1 equivalent of HO-R ₂ -OH was added to react according to the following Reaction Scheme 4, and R ₁ COOCH ₃ Specific reaction and purification conditions are the same as those described in Preparation Example 1, except that the molar ratio of and HO-R ₂ -OH was reacted at 4:1.

[Scheme 4]

In the above, R ₁ COOCH ₃ used methyl octanoate, methyl decanoate, methyl dodecanoate, and tetradecanoate, and HO-R ₂ -OH is ethylene glycol, diethylene glycol, triethylene glycol, PEG 200 (TCI, product number P0840), PEG 400 (TCI, product number N0443) and PEG 600 (TCI, product number N0443) were used.

Example 3. Measurement of phase transition temperature and latent heat of diester PCM

The phase transition temperature and latent heat of the diester PCM synthesized according to the method described in Example 3 were measured according to the method described in Example 2, and the lowest and highest temperatures according to R ₁ are shown in Table 4 below.

R ₁ COO- Minimum temperature (℃) Maximum temperature (℃) Octanoate -70 40 Decanoate -40 70 Dodecanoate -20 80 Tetradecanoate -10 90

The measured phase transition temperature and latent heat values are shown in Table 5 below.

* In the above table, C8, C10, C12 and C14 represent the carbon number of R ₁ COO- in the ester among the reactants of Scheme 3.

For example, for purposes of claim construction, the claims set forth below should not be interpreted in any way narrower than their literal language, and therefore, exemplary embodiments from the specification should not be read as claims. Accordingly, it should be understood that the invention has been described by way of illustration and not limitation on the scope of the claims. Accordingly, the invention is limited only by the following claims. All publications, patents, patent applications, books and journal articles cited in this application are hereby incorporated by reference in their entirety.

Claims (10)

A composition for temperature control comprising a compound represented by Formula 1 or a compound represented by Formula 2 or both as a phase change material:
[Formula 1]

(In the above formula 1
R ₁ is a straight-chain or ground type C _m H _2m+1 -,
R ₂ is C _n H _2n+1 (O(CH ₂ ) ₂ ) _p -,
m is an integer from 5 to 20,
n is an integer from 1 to 5,
p is an integer from 0 to 3.)
[Formula 2]

(In the formula 2 above
R1 is a straight chain or pulverized C _q H _2q+1 -,
R ₂ is -((CH ₂ ) ₂ O) _r (CH ₂ ) ₂ -,
q is an integer from 5 to 15,
r is an integer from 0 to 14.). The method according to claim 1, p and r are each non-zero composition The composition according to claim 1 or 2, wherein the phase transition temperature is -20°C to 70°C. The method according to claim 1 or 2, In Formula 1 R ₂ CH ₃ OC ₂ H ₄ -, CH ₃ (OC ₂ H ₄ ) ₂ -, CH ₃ (OC ₂ H ₄ ) ₃ -, C ₂ H ₅ OC ₂ H ₄ -, C ₂ H ₅ (OC ₂ H ₄ ) ₂ -, C ₂ H ₅ (OC ₂ H ₄ ) ₃ -, C ₄ H ₉ OC ₂ H ₄ -, C ₄ H ₉ (OC ₂ H ₄ ) ₂ Any one selected from the group consisting of -, and R ₁ is any one selected from the group consisting of a straight chain C ₁₂ H ₂₅ -, C ₁₄ H ₂₉ -, C ₁₆ H ₃₃ -, C ₁₈ H ₃₇ -,
In Formula 2, R ₂ is -C ₂ H ₄ OC ₂ H ₄ -or -C ₂ H ₄ (OC ₂ H ₄ ) ₂ -, and in Formula 2, R ₁ is a straight chain C ₈ H ₁₇ -, C ₁₀ H _21- , C ₁₂ H ₂₅ -, C ₁₄ H ₂₉ -is any one selected from the group consisting of. R ₁ COOCH ₃ and R ₂ -OH using dibutyltin oxide (DBTO) as a catalyst; Or R ₁ COOCH ₃ , and HO-R ₂ -OH, comprising the steps of reacting, to prepare a compound represented by Formula 1 or a compound represented by Formula 2:
[Formula 1]

(In the above formula 1
R ₁ is a straight-chain or ground type C _m H _2m+1 -,
R ₂ is C _n H _2n+1 (O(CH ₂ ) ₂ ) _p -,
m is an integer from 5 to 20,
n is an integer from 1 to 5,
p is an integer from 0 to 3.)
[Formula 2]

(In the formula 2 above
R1 is a straight chain or pulverized C _q H _2q+1 -,
R ₂ is -((CH ₂ ) ₂ O) _r (CH ₂ ) ₂ -,
q is an integer from 5 to 15,
r is an integer from 0 to 14.). The method according to claim 5, wherein R ₁ COOCH ₃ :R ₂ -OH or R ₁ COOCH ₃ :HO-R ₂ -OH is 1:1 to 1:8 (mol:mol). The method of claim 5 or 6, wherein the reaction is performed at 100 mbar to 500 mbar. The method of claim 5 or 6, wherein the reaction is performed at 120°C to 150°C. The method of claim 5, wherein p and r are each non-zero. An article comprising the composition of claim 1 or 2.

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