KR101083817B1 - Nano-encapsulated phase change material hybrid polyurethane emulsion and preparation method thereof - Google Patents

Abstract

The present invention relates to a nano-encapsulated phase change material (PCM) hybrid polyurethane emulsion and a method for preparing the same, and hybridizes nano-encapsulated encapsulated phase change material prepared using a mini emulsion synthesis method to polyurethane. It is characterized in that the phase change material is present in a stable state, the nano-encapsulated phase change material hybrid polyurethane emulsion according to the present invention can be usefully used in latent heat functional material that requires heat retention.

Description

Polyurethane emulsion hybrid with phase change material nanocapsules and preparing method of the same}

The present invention relates to a nano-encapsulated phase change material (PCM) hybrid polyurethane emulsion and a method for preparing the same, and more particularly, to a nano-particle-sized encapsulated phase change material prepared using a mini emulsion synthesis method. The present invention relates to a hybridization by dispersing a polyurethane so that the phase change material is present in a stable state. The nano-encapsulated phase change material hybrid polyurethane emulsion according to the present invention can be applied to latent heat functional materials that require heat retention, in particular functional fiber materials, building interior and exterior materials, energy storage media, heat storage materials, electronic materials It can be usefully used.

As oil and coal are gradually depleted, many countries have been trying to solve energy problems for a long time, and researches on new energy sources are actively conducted to solve energy problems. However, first of all, research that can generate the largest energy efficiency with the same amount of energy is urgently required.

In order to maximize efficiency, the method of adding a new heat transfer medium having a high heat capacity is most effective. Research on such heat transfer media has been steadily progressing, and in recent years, many research capabilities have been concentrated on latent heat storage methods using phase change materials (PCMs). A phase change material is a material that absorbs or releases a lot of heat while changing phase at a specific temperature without changing the temperature. The heat absorbed or released is called latent heat. The latent heat storage, which is one of energy storage methods, is a heat storage method using heat that is absorbed or released at isothermal when a phase of a material changes, that is, latent heat.

In the heat storage method using latent heat, the phase change material usually has a melting temperature (℃) of -10 ~ 60 ℃. Therefore, it is difficult to apply to real life by forming and processing the outflow of phase change material by liquefaction according to temperature change. Have.

Therefore, the inventors of the present invention sought to apply the phase change material to daily life usefully, and thus, the polyurethane was maintained in a stable state in the phase change material encapsulated in nano particle size to increase the surface area of the existing micro particle size. The present invention was completed by finding a method for preparing an encapsulated phase change material hybrid polyurethane emulsion having a nanoparticle size to increase the utilization thereof by exerting excellent latent heat characteristics by hybridizing the same.

Accordingly, the present invention provides a method for preparing a nano-encapsulated phase change material hybrid polyurethane emulsion which can be hybridized by dispersing polyurethane in a stable state in a nano-encapsulated phase change material prepared using a mini emulsion synthesis method. There is this.

Another object of the present invention is to provide a method for preparing a nanoencapsulated phase change material hybrid polyurethane emulsion capable of improving dispersion stability in a nanoencapsulated phase change material of polyurethane.

It is another object of the present invention to provide a phase change material hybrid polyurethane emulsion encapsulated in nanoparticle size produced by the above method.

It is another object of the present invention to provide a latent heat functional material including the nano-encapsulated phase change material hybrid polyurethane emulsion.

In order to achieve the above object, the present invention comprises the steps of preparing a polyurethane prepolymer by adding dimethylolpropionic acid (DMPA) and an isocyanate compound to the polyol and then reacting with a neutralizing agent; Dissolving a phase change material in a mixture of a polymer monomer and an emulsifier, and emulsifying it in water containing an emulsifier, and then adding an initiator to polymerize to prepare a nano-encapsulated phase change material; A dispersion step of dispersing the polyurethane prepolymer in a solution containing the nanocapsule phase change material; It provides a method for producing a nano-encapsulated phase change material hybrid polyurethane emulsion comprising the step of polymerizing by adding a chain extender to the dispersed emulsion.

According to the present invention, the prepolymer preparing step may include adding 5 to 10 parts by weight of dimethylolpropionic acid (DMPA) and an isocyanate compound to 100 parts by weight of a polyol having a number average molecular weight of 500 to 3,000, and then neutralizing agent. It is characterized by the addition.

According to the present invention, the isocyanate compound in the prepolymer preparation step is characterized in that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) to the hydroxyl group (OH) of the polyol is 1.8 to 2.2.

According to the present invention, the neutralizing agent in the prepolymer preparation step is characterized in that the molar ratio of the neutralizing agent to dimethylol propionic acid (neutralizing agent / DMPA) is added so that 0.7 to 1.0.

According to the present invention, the nano-encapsulated phase change material manufacturing step dissolves 100 parts by weight of a phase change material in a mixture of 70 to 120 parts by weight of a polymer monomer and 60 to 100 parts by weight of an emulsifier, and includes 1 to 5 parts by weight of an emulsifier. Emulsified into 800 to 1000 parts by weight, and then 0.5 to 2 parts by weight of the initiator is added, characterized in that for polymerization.

According to the present invention, the phase change material in the nanoencapsulated phase change material manufacturing step is n-octacoic acid, n-heptacoic acid, n-hexacoic acid, n-tetracoic acid, n-tricoic acid, n-docoic acid, n At least one selected from the group consisting of hehenicoic acid, n-icoic acid, n-nonadecane, n-octadecane, n-heptadecane, n-hexadecane, n-pentadecane, n-tetradecane and n-tridecane It is characterized by using one.

According to the present invention, cetyl alcohol or stearyl alcohol is used as the emulsifying aid in the nanoencapsulated phase change material manufacturing step.

According to the present invention, the emulsification in the step of preparing nano-encapsulated phase change material is emulsified by stirring at 5,000 to 12,000 rpm for 5 to 30 minutes using a homogenizer, or 50 to 500 watts of strength at 5 to 30 minutes using an ultrasonic wave. It is characterized in that the processing by (amplitude).

According to the present invention, at least one selected from potassium percellate (Potassiumpersulfate; KPS), aminopropanesulfonic acid (APS) or azobis methylpropionitrile (AIBN) in the nanoencapsulated phase change material manufacturing step It characterized in that to use.

According to the present invention, the dispersing step is characterized in that it is slowly added in a ratio of 40 to 70 parts by weight of the polyurethane prepolymer solution with respect to 100 parts by weight of a solution containing a nano-encapsulated phase change material.

According to the present invention, the chain extender is a compound containing at least two primary or secondary amino groups or hydroxyl groups, such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, ethylenediol, propylenediol, At least one selected from butylenediol, pentylenediol, and hexamethylenediol is used.

According to the present invention, the chain extender is added in an amount of 1 to 5 parts by weight based on 100 parts by weight of the polyurethane prepolymer.

In order to achieve another object of the present invention, the present invention provides a nano-encapsulated phase change material hybrid polyurethane emulsion, characterized in that prepared by the above production method.

In order to achieve another object of the present invention, the present invention is characterized in that the functional fiber material, building interior and exterior materials, energy storage medium, heat storage material or electronic material includes the nanoencapsulated phase change material hybrid polyurethane emulsion of claim 12. It provides a latent heat functional material.

The present invention is stable in the process of preparing a nano-encapsulated phase change material hybrid polyurethane emulsion by dispersing the polyurethane in the phase change material encapsulated in the nano-particle size prepared by the mini-emulsion synthesis method. It can be present, and has a useful effect of providing a nano-encapsulated phase-change material hybrid polyurethane emulsion to exhibit the latent heat characteristics than the micro-particle size to increase the utilization of the phase-change material and to ensure sufficient thermal insulation properties.

Hereinafter, the present invention will be described in more detail.

First, a method of preparing a mixed polyurethane emulsion according to the present invention will be described. In the present invention, a polyurethane prepolymer is prepared by adding dimethylolpropionic acid and an isocyanate compound to a polyol and reacting, followed by adding a neutralizing agent (A), (B) preparing a nano-encapsulated phase change material by polymerizing a mixed solution of a polymer monomer and an emulsion adjuvant in a mixture solution in which a phase change material is dissolved in water containing an emulsifier, and then emulsifying with an initiator. Preparation of nano-encapsulated phase change material hybrid polyurethane emulsion comprising a dispersion step (C) of dispersing the polyurethane prepolymer in a solution containing a material and a step (D) of polymerizing a chain extender into the dispersed emulsion Provide a method.

(A) Polyurethane prepolymer manufacturing step

Polyurethane prepolymer manufacturing step according to the present invention is to add a neutralizing agent after the reaction by adding dimethylol propionic acid and isocyanate compound to the polyol.

More specifically, in the present invention, 5 to 10 parts by weight of dimethylolpropionic acid (DMPA) and an isocyanate compound are added to 100 parts by weight of a polyol having a number average molecular weight of 500 to 3000, and then a neutralizer is added to the polyol. Urethane prepolymer is prepared. At this time, the isocyanate compound is added such that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) is 1.8 to 2.2 with respect to the hydroxyl group (OH) of the polyol. In addition, the neutralizing agent is added so that the molar ratio (neutralizing agent / DMPA) to DMPA is 0.7 to 1.0.

Here, the polyol has a number average molecular weight of 500 to 3000, but if the number average molecular weight of the polyol is less than 500, the dispersion stability and processability is inferior, and if the number average molecular weight exceeds 3000, the overall physical properties are deteriorated. . Therefore, it is preferable to use a polyol having a number average molecular weight within the above range. More preferably, the number average molecular weight is 1000 to 2500.

As the polyol, polyester polyol, carbonate polyol, caprolactone polyol and the like can be used. Preferably, polyester polyols are used.

Polyester polyols are generally commercially available and are obtained by condensation of diacids or acid anhydrides with glycols. Diacids can be used either saturated or unsaturated and alkyl or cyclic alkyl and phenyl. Examples include phthalic acid, hydrozinnate phthalic acid, isoplic acid, tellaflic acid, malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, sublic acid, azeratic acid, sebacic acid, formic acid, succinic anhydride , Phthalic anhydride, maleic anhydride, hydrozinnate phthalic anhydride and the like. Alkyl glycols are generally used as glycols. Examples thereof include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl propane glycol, neopentyl glycol, butylethyl flopane glycol, butanediol, hexane diol and the like.

In the case of carbonate polyols, commercially available PCDLs from Asahi Kasai can be used.

In the case of caprolactone-based polyols, epsilon caplolactone-modified products can be used, and the commercialized lactone polyol Placcel 200 series of Daicel can be optionally used.

Dimethylolpropionic acid added to the polyol is used to introduce a hydrophilic group, and when the amount is less than 5 parts by weight with respect to 100 parts by weight of polyol, smooth water dispersion is difficult and the stability is low, and the amount of the added 10 If it exceeds the weight part, there is a disadvantage that the chemical resistance is lowered. Therefore, it is preferable to add 5-10 weight part of dimethylol propionic acids with respect to 100 weight part of polyols.

In this case, the dimethylol propionic acid may be added in a dissolved state in a solvent, for example, may be added by dissolving in a solvent such as N-methyl-2-pyrrolidone, methanol or ethanol, and the solvent is dimethylolpropy. 120 parts by weight or more, preferably 120 to 200 parts by weight, based on 100 parts by weight of onic acid, can be dissolved.

According to the present invention, an isocyanate compound which reacts with the polyol to form a polyurethane is used. Preferably, the equivalent ratio (NCO / OH) of the isocyanate group (NCO) is 1.8 to the hydroxyl group (OH) of the polyol. It is added so that it becomes an equivalent ratio of 2.2. When the equivalent ratio (NCO / OH) of the isocyanate group (NCO) is less than 1.8 with respect to the hydroxy group (OH) of the polyol, there is a problem in that the urethane bond is small and the flexibility is insufficient, and the tension is decreased. If the equivalent ratio (NCO / OH) of NCO (2.2) exceeds 2.2, there is a problem that the workability is not good because the viscosity of the reactant increases.

At this time, the reaction is carried out for 3 hours or more in the state of raising the temperature of the reactor to 70 to 100 ℃, the end of the reaction can be easily confirmed through the change in the absorption band length of the isocyanate group (NCO), for example in the IR spectrum, etc. have.

Isocyanates can use all of the most commonly used isocyanates, but it is preferable to use diisocyanate. As the diisocyanate, those selected from toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate, hexane diisocyanate, hexamethylene diisocyanate and the like can be used.

In order to promote the reaction, a catalyst used in preparing a conventional polyurethane may be added within a conventional addition range, and a usable catalyst is dibutyltin dilaurate (DBDTL).

Neutralization is carried out by adding the neutralizing agent to pH 7-10 while cooling the temperature of the reaction vessel to 50-70 ° C. More preferably, the neutralizing agent is added so that the molar ratio (neutralizing agent / DMPA) relative to DMPA is 0.7 to 1.0. When added within this range, the particle size of the finally prepared hybrid emulsion is maintained in a small state to improve stability.

The neutralizing agent may be ammonia, ethylamine, butylamine, dimethylamine, diisopropylamine, dimethylethylamine, benzylamine, ethanolamine, diethanolamine, triethanolamine, tributylamine, methyl diethanolamine, diethylethanolamine, Dimethylethanolamine, normal methylmorpholine, diisopropanolamine or 2-amino2-methyl1-propanol may be used, and preferably diethylethanolamine is used.

(B) step of preparing a phase change material encapsulated in nanoparticle size

The manufacturing step of the nano-encapsulated phase change material according to the present invention consists of dissolving the phase change material in a polymer monomer and an emulsifier adjuvant, putting it in water containing an emulsifier and emulsifying it, followed by polymerization with an initiator.

More specifically, in the present invention, 100 parts by weight of the phase change material is dissolved in a mixture of 70 to 120 parts by weight of a polymer monomer and 6 to 10 parts by weight of an emulsifier, and then emulsified into 600 to 1000 parts by weight of water containing 1 to 5 parts by weight of an emulsifier. After adding 0.5 to 2 parts by weight of the initiator, and then polymerized to prepare a nano-encapsulated phase change material in an emulsion state.

 In the present invention, "Phase Change Material (PCM)" is also referred to as "latent heat storage material" or "latent heat storage material" and absorbs heat energy while changing from solid phase to liquid phase or liquid phase to solid phase within a certain temperature range. Means a substance that emits.

These phase change materials can be selected from known ones, but preferably n-octacoic acid, n-heptacoic acid, n-hexacoic acid, n-tetracoic acid, n-tricoic acid, n-docoic acid, n- At least one selected from the group consisting of heneicoic acid, n-icoic acid, n-nonadecane, n-octadecane, n-heptadecane, n-hexadecane, n-pentadecane, n-tetradecane and n-tridecane Can be used.

As the polymer monomer coating the surface of the phase change material, any polymer monomer commonly used to coat a phase change material in the art may be used, and preferably, melamine resin, urea resin, gelatin, cellulose, epoxy, poly At least one polymer selected from the group consisting of urethane, polyamide, polyethylene, polymethylmethacrylate, polyester, polystyrene and polyvinyl alcohol can be used.

The polymer monomer is preferably added 70 to 120 parts by weight based on 100 parts by weight of the phase change material. If the addition amount of the polymer monomer is less than 70 parts by weight, the problem of not encapsulating the phase change material occurs, and if the addition amount is more than 120 parts by weight, the thickness of the capsule becomes thick, resulting in a significant drop in latent heat characteristics.

Emulsification aids are added to maintain a stable emulsified state, it is applicable to those commonly used in the art. Long-chain alcohols such as cetyl alcohol or stearyl alcohol may be used as the emulsification aid, and more preferably cetyl alcohol may be used.

The emulsification aid is used 60 to 100 parts by weight based on 100 parts by weight of the phase change material, if the amount is less than 60 parts by weight of the capsule size increases the problem that the stability is reduced, the amount is 100 parts by weight If exceeded, the latent heat characteristic is deteriorated.

The emulsifier may be any one generally used in the art, and preferably anionic surfactants are used. The anionic surfactant may be selected and used in general, for example, those selected from carboxylate, sulfonate, sulfate ester salt and phosphate ester salt may be used. The carboxylates include higher fatty acid alkali salts, N-acrylic amino acid salts, alkyl ether carbonates, and acylated peptides, and sulfonate salts include alkyl sulfonates, alkylbenzenes and alkylamino acid salts, alkylnaphthalene sulfonate salts, and sulfo pumpkin salts. The sulfate ester salts include alkyl sulfates, alkyl ether sulfates, alkylaryl ether sulfates, alkylamide sulfates, and the like, and the phosphate ester salts include alkyl phosphates, alkyl ether phosphates, and alkylaryl ether phosphates.

The emulsifier will be used in 1 to 5 parts by weight based on 100 parts by weight of the phase change material. If the amount of the emulsifier is less than 1 part by weight, the particles of the capsules are large, and if the amount is more than 5 parts by weight, the latent heat characteristic is deteriorated.

Water does not limit the amount used, but in consideration of workability, it is preferable to use 600 to 1000 parts by weight based on 100 parts by weight of phase change material.

The emulsification method is not necessarily limited when emulsifying the above-described phase change material in the polymer monomer and the emulsifier adjuvant mixture in water containing the emulsifier, various methods can be applied. For example, a homogenizer or an ultrasonic wave can be used. In the case of using a homogenizer, it can be stirred at 5,000 to 12,000 rpm for 5 to 30 minutes, and in the case of using an ultrasonic wave, it can be emulsified by treating at an amplitude of 50 to 500 watts for 5 to 30 minutes.

An initiator is added to enable encapsulation of the phase change material as the polymer monomer polymerizes. As the initiator, an initiator commonly used in the art may be used. For example, potassium percellate (KPS), aminopropanesulfonic acid (APS), azobismethylpropionitrile (AIBN) ) May be used. It is preferable to use potassium persulfate.

The initiator is added to 0.5 to 2 parts by weight based on 100 parts by weight of the phase change material, when the addition amount is less than 0.5 parts by weight polymerization of the monomer is not made smoothly occurs a problem that can not be encapsulated, the addition amount 2 If it exceeds the weight part, it is preferable to add it within the above range because it causes a problem of stability due to a faster polymerization rate than necessary.

The reaction temperature in the polymerization reaction is 60 to 80 ℃, preferably about 70 ℃ 2 to 6 hours, preferably about 4 hours to obtain a nano-encapsulated phase change material. The particle size of the obtained capsule is about 5 to 500 nanometers.

(C) dispersion step

The dispersing step is to disperse the polyurethane prepolymer in a solution containing the nanocapsule phase change material. Dispersion can be carried out in-situ without a separate separation process, and it is obvious that it can also be carried out by a method other than in-situ if necessary. Dispersion is made by gradually adding in a proportion of 40 to 70 parts by weight of the polyurethane prepolymer solution with respect to 100 parts by weight of the solution containing the nano-encapsulated phase change material with continuous stirring.

(D) polymerization step by chain extender

The polymerization step by the chain extender is to polymerize by adding a chain extender to the dispersed emulsion.

The chain extender may use diamines and diol compounds, specifically, a compound containing two primary or secondary amino groups and two hydroxyl groups, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine , Ethylenediol, propylenediol, butylenediol, pentylenediol, hexamethylenediol can be used by mixing at least one or more.

The chain extender is preferably added 1 to 5 parts by weight based on 100 parts by weight of the polyurethane prepolymer. In addition, the chain extender is preferably added after dilution in a small amount of water.

Various additives may be further added within a range that does not change the properties of the present invention in the dispersing step before the chain extender is added. Antioxidants, UV absorbers, light stabilizers, thermal polymerisation inhibitors, leveling agents, including, for example, antistatic agents selected from conductive polymers, quaternary ammonium salts, inorganic salts, metal particles, (meth) acrylate modified quaternary ammonium salts , Surfactants, lubricants and the like may additionally be used within the usual addition range.

When the chain extender is added and polymerized, a polyurethane emulsion in which the nanoencapsulated phase change material according to the present invention is mixed can be obtained. The polyurethane emulsion thus obtained is present while the phase change material encapsulated in the mixed nanoparticle size is maintained in a stable state and excellent latent heat characteristics.

Therefore, the present invention provides a nano-encapsulated phase change material hybrid polyurethane emulsion prepared by the method according to the present invention described above. The emulsion thus prepared can be applied to a variety of products that require heat retention through its own or separate post-processing, and in particular, latent functional materials such as functional textile materials, building interior and exterior materials, energy storage media, heat storage materials, and electronic materials. It can be usefully used.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention and the present invention is not limited thereto.

≪ Example 1 >

A polyol methylene adipate with a number average molecular weight of 2,000 g was added to a 1000 mL four-neck double jacketed reactor connected with a condenser and a stirrer, and then dissolved at 80 ° C. After dissolving the polyol, isophorone diisocyanate was polymerized while adding 35.1 g with DB5 0.005 g so that the equivalent ratio of NCO groups to OH of the polyol was 2.0. Then, 4 g of dimethylol propionic acid (DMPA) having a hydrophilic group was dissolved in 11 g of NMP, and then stirred for 80 minutes. After the reaction, the temperature was lowered to 60 ° C. and 3.02 g of triethylamine (TEA) to 1.0 was added so that the molar ratio (TEA / DMPA) of DMPA was 1.0 to neutralize the carboxyl group of DMPA for 20 minutes to prepare a polyurethane prepolymer.

Separately, 25 g of Octadecane maintained at 50 ° C. were dissolved in a mixture of 25 g of styrene monomer and 2 g of cetyl alcohol, which was then dispersed by slowly adding 0.7 g of sodium lauryl sulfate to a solution of 200 g of water, followed by homogenizer ( Homogenizer IKA T-50 basic) was forced to emulsify at 10,000 rpm for 10 minutes. Subsequently, 0.25 g of potassium persulfate was added to the emulsion, and polymerization was performed at 70 ° C. for 4 hours to prepare an nanocapsule-encapsulated phase change material in an emulsion state.

The dispersion process was performed while slowly adding at a rate of 50 g of the polyurethane prepolymer prepared above while stirring at a rate of 500 rpm with respect to 100 g of the solution of the nanoencapsulated phase change material.

Thereafter, 2 g of ethylenediamine (EDA) was added to 8 g of ultrapure water, and the diluted solution was added to the reaction solution in which the water dispersion step was completed, followed by stirring for 2 hours to prepare a nanoencapsulated phase change material hybrid polyurethane emulsion.

<Examples 2 to 8>

The same procedure as in Example 1 was conducted except that the addition amount of isophorone diisocyanate and TEA was changed so that the equivalent ratio of NCO groups to OH of polyol and TEA to DMPA was as shown in Table 1 below. An encapsulated phase change material hybrid polyurethane emulsion was prepared.

Experimental Example 1

Using the nano-encapsulated phase change material hybrid polyurethane emulsion prepared in Examples 1 to 8 was carried out to evaluate the physical properties as shown in Table 1 below.

1. The particle size of nanocapsules

The particle size of the prepared nanocapsules was measured by dilution with ultrapure water at 25 ° C. using capillary hydrodynamic fractionation (CHDF2000, Matee Applied Sience, U.S.A.).

2. Particle Size Size of Urethane Emulsion

The particle size of the urethane emulsion was measured by dilution with ultrapure water at 25 ° C. using capillary hydrodynamic fractionation (CHDF2000, Matee Applied Sience, U.S.A.). In order to confirm the size change, the measurement results are expressed as average particle size.

3. Energy storage capacity (polyurethane emulsion)

A nano-encapsulated phase change material hybrid polyurethane emulsion was placed in a silicone coated mold and cured to prepare a film having a thickness of 10 mm. The film thus prepared was subjected to an energy storage capacity using a Differential Scanning Calorimeter (DSC Q10, T.A. Instruments Inc., USA).

4. Tension

The film obtained by drying the nanoencapsulated phase change material hybrid polyurethane emulsion at 80 ° C. for two hours was measured using a Universal Testing Machine (UTM, Instron Co., USA).

5. Stability

The prepared nano acrylic mixed water dispersion polyurethane composition was stored at room temperature for 6 months, and then the presence or absence of precipitation was evaluated to evaluate the dispersion and storage stability.

division NCO / OH TEA /
DMPA Capsule size
(nm) Emulsion Average
Particle size (nm) tension
(MPa) Energy storage efficiency stability
(Precipitation) Example 1 1.6 1.0 / 1.0 20-100 68 1.8 77.76 radish Example 2 1.8 1.0 / 1.0 20-100 77 2.9 82.76 radish Example 3 2.0 1.0 / 1.0 20-100 82 4.2 88.36 radish Example 4 2.2 1.0 / 1.0 20-100 98 4.4 95.45 radish Example 5 2.4 1.0 / 1.0 20-100 122 4.0 81.43 radish Example 6 2.0 0.5 / 1.0 20-100 153 2.6 67.72 U Example 7 2.0 0.70 / 1.0 20-100 96 3.5 77.67 radish Example 8 2.0 0.85 / 1.0 20-100 93 4.1 84.46 radish Example 9 2.0 1.2 / 1.0 20-100 83 4.4 85.48 U

As shown in Table 1, in the case of Examples 2 to 4 in which the ratio of NCO / OH is the preferred range of the present invention, the emulsion particle size is low, the tension is excellent, the energy storage efficiency is excellent, and the storage is higher than Examples 1 and 5. It can be confirmed that the stability is excellent.

In addition, in Examples 3, 7, and 8, where the ratio of TEA / DMPA is in the preferred range of the present invention, the emulsion particle size and the storage stability are lower than those of Examples 6 and 9, in which the ratio of TEA / DMPA is outside the preferred range of the present invention. It can be confirmed that excellent.

Claims (14)

Preparing a polyurethane prepolymer by adding dimethylolpropionic acid (DMPA) and an isocyanate compound to the polyol, followed by reaction with a neutralizing agent; Dissolving a phase change material in a mixture of a polymer monomer and an emulsifier, and emulsifying it in water containing an emulsifier, and then adding an initiator to polymerize to prepare a nano-encapsulated phase change material; Dispersing the polyurethane prepolymer in a solution containing the nanocapsule phase change material; And And polymerizing by adding a chain extender to the dispersed emulsion, The phase change material is n-octacoic acid, n-heptacoic acid, n-hexacoic acid, n-tetracoic acid, n-tricoic acid, n-docoic acid, n-heneicoic acid, n-icoic acid, n-nona At least one selected from the group consisting of decane, n-octadecane, n-heptadecane, n-hexadecane, n-pentadecane, n-tetradecane and n-tridecane, The polymer monomer is at least one selected from the group consisting of melamine resin, urea resin, gelatin, cellulose, epoxy, polyurethane, polyamide, polyethylene, polymethyl methacrylate, polyester, polystyrene and polyvinyl alcohol Method for producing a nano-encapsulated phase change material hybrid polyurethane, characterized in that the monomer. The method of claim 1, The prepolymer manufacturing step is characterized by adding a neutralizing agent after the reaction by adding 5 to 10 parts by weight of dimethylolpropionic acid (DMPA) and an isocyanate compound to 100 parts by weight of polyol having a number average molecular weight of 500 to 3000 Nano-encapsulated phase change material hybrid polyurethane production method. 3. The method of claim 2, The isocyanate compound in the prepolymer preparation step is nano-encapsulated phase change material hybrid polyurethane, characterized in that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) to 1.8 to 2.2 to the hydroxyl group (OH) of the polyol Manufacturing method. 3. The method of claim 2, In the prepolymer manufacturing step, the neutralizing agent is a nano-encapsulated phase change material hybrid polyurethane manufacturing method characterized in that the molar ratio (neutralizing agent / DMPA) of the neutralizing agent to dimethylol propionic acid is added to be 0.7 to 1.0. The method of claim 1, The nano-encapsulated phase change material manufacturing step dissolves 100 parts by weight of a phase change material in a mixture of 70 to 120 parts by weight of a polymer monomer and 60 to 100 parts by weight of an emulsifier, and 800 to 1000 parts by weight of water containing 1 to 5 parts by weight of an emulsifier. The method for producing a nano-encapsulated phase change material hybrid polyurethane, characterized in that the polymerization is carried out by adding the emulsifier in 0.5 parts to 2 parts by weight. delete The method of claim 5, Cetyl alcohol (stetyl alcohol) or stearyl alcohol (stearyl alcohol) as the emulsification aid nano-encapsulated phase change material hybrid polyurethane manufacturing method characterized in that using. The method of claim 5, The emulsification is emulsified by stirring at 5,000 to 12,000 rpm for 5 to 30 minutes using a homogenizer, or nano-encapsulated, characterized in that the treatment with an amplitude of 50 to 500 watts for 5 to 30 minutes using an ultrasonic wave Phase change material hybrid polyurethane manufacturing method. The method of claim 5, The initiator is nano-encapsulated phase change material, characterized in that using at least one selected from potassium persulfate (KPS), aminopropanesulfonic acid (APS) or azobis methylpropionitrile (AIBN) Hybrid polyurethane production method. The method of claim 1, The dispersing step is a nano-encapsulated phase change material hybrid polyurethane manufacturing method characterized in that the input is made by the ratio of 40 to 70 parts by weight of the polyurethane prepolymer solution with respect to 100 parts by weight of a solution containing a nano-encapsulated phase change material. The method of claim 1, The chain extender is a compound containing at least two primary or secondary amino groups or hydroxyl groups, such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, ethylenediol, propylenediol, butylenediol, Method for producing a nano-encapsulated phase change material hybrid polyurethane, characterized in that at least one selected from pentylenediol, hexamethylenediol. The method of claim 11, The chain extender is a method for producing a nano-encapsulated phase change material hybrid polyurethane, characterized in that 1 to 5 parts by weight based on 100 parts by weight of polyurethane prepolymer. delete delete