CN111534285A - SiO (silicon dioxide)2Preparation method of modified phase-change microcapsule - Google Patents
SiO (silicon dioxide)2Preparation method of modified phase-change microcapsule Download PDFInfo
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- CN111534285A CN111534285A CN202010484843.9A CN202010484843A CN111534285A CN 111534285 A CN111534285 A CN 111534285A CN 202010484843 A CN202010484843 A CN 202010484843A CN 111534285 A CN111534285 A CN 111534285A
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Abstract
The invention discloses a SiO2A preparation method of a modified phase-change microcapsule belongs to the field of phase-change material energy storage. The preparation method comprises the following steps: firstly, SiO is firstly2Formaldehyde solution, melamine, triethanolamine and the like are stirred and mixed under certain conditions to prepare SiO2Modified melamine resin prepolymer solution; then stirring and mixing the phase-change material and the emulsifier under certain conditions to prepare emulsion; finally, the prepared prepolymer solution and the emulsion are subjected to in-situ polymerization reaction, and SiO is prepared after washing, filtering and drying2Modified phase change microcapsules. Compared with the prior art, the preparation method is environment-friendly, simple in process and low in cost, the obtained phase-change microcapsule is spherical, good in heat storage performance, high in phase-change latent heat, high in capsule wrapping rate, excellent in overall structure and thermal stability, and can be widely applied to the fields of solar energy, buildings, textiles, military affairs and the like.
Description
Technical Field
The invention relates to SiO2A preparation method and application of a modified phase-change microcapsule belong to the technical field of phase-change energy storage materials.
Technical Field
Since the new century, with the development of society, the progress of industry and the increase of economy, the problem of energy becomes increasingly serious. Therefore, development and utilization of new energy, improvement of energy utilization efficiency, and effective storage of energy have become hot spots for researchers. The phase-change material can absorb and release a large amount of heat in the phase-change process, and can play a role in controlling temperature and storing energy.
Phase change microcapsules refer to the process of coating dispersed particle droplets with a continuous film to obtain nano-to micron-sized capsules. The phase-change microcapsule is composed of a core (core material) and a shell (polymer or inorganic wall material). The phase change microcapsules may be formed into regular shapes. Such as spherical or elliptical, and may also take on irregular shapes. After the phase change material (core material) is wrapped by the wall material, the microcapsule is formed, and the microcapsule has a high specific surface area, so that the leakage of the phase change material can be prevented, the heat energy storage and release efficiency can be increased, the change of the volume of the core material in the phase change process can be borne, and the core material in the microcapsule can be protected.
SiO2Has the advantages of ultraviolet resistance, high mechanical property, good compatibility, high heat conductivity coefficient and the like, and simultaneously, SiO2Is nontoxic and pollution-free, and is a good choice for improving the mechanical property of the microcapsule as a modifier.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a SiO microcapsule aiming at the technical problems of poor heat storage performance, low latent heat of phase change and low wrapping rate in the existing phase change microcapsule and the preparation process thereof2Preparation method of modified phase change microcapsule, SiO of the invention2The modified phase-change microcapsule not only enhances the heat storage performance, but also improves the phase-change latent heat and the wrapping rate of the phase-change microcapsule. SiO of the invention2The modified phase-change microcapsule has the characteristics of good thermal stability and high heat storage capacity. The preparation method is simple and easy to control.
The technical scheme is as follows: the invention provides SiO2The preparation method of the modified phase-change microcapsule is a regular spherical shape and has a core-shell structure, wherein the core-shell structure consists of a wall material, a core material and an emulsifier for connecting the wall material and the core material, the wall material is melamine resin, the core material is a phase-change material, and the modifier is SiO2And SiO2The emulsifier, the melamine resin and the paraffin are in a mass ratio of (1-5%): (0.5-5%): (5-50%): 100 percent
Wherein:
the SiO2The size is 1 nm-100 um.
The emulsifier is one or more than two of styrene-maleic anhydride copolymer, sodium dodecyl benzene sulfonate and polyoxyethylene octyl phenol ether-10.
The melamine resin is polymerized by melamine and formaldehyde solution.
The phase-change material is paraffin, fatty acid, tetradecanol, hexadecanol or polyethylene glycol.
SiO (silicon dioxide)2The preparation method of the modified phase-change microcapsule comprises the following steps:
1) deionized water and SiO2Stirring and mixing the formaldehyde solution, the melamine and the triethanolamine under an alkaline condition; to obtain SiO2Modified melamine resin prepolymer;
2) dispersing and emulsifying deionized water, a phase-change material and an emulsifier under an acidic condition to obtain an emulsion;
3) slowly dripping the prepolymer obtained in the step 1) into the emulsion obtained in the step 2), stirring the emulsion simultaneously until the prepolymer is completely dripped into the emulsion, continuously stirring for 2 hours, and adjusting the mixed solution to be in an alkaline state to obtain SiO2A modified phase change microcapsule slurry;
4) filtering, washing and drying to obtain SiO2Modified phase change microcapsules.
Wherein:
the dispersing and mixing time in the step 1) is 10-100 minutes, the temperature condition is 25-80 ℃, and the stirring speed is 100-3000 r/min;
the emulsification time in the step 2) is 10-150 minutes, the temperature condition is 25-80 ℃, and the stirring speed is 100-20000 revolutions per minute;
the stirring time in the step 3) is 10-300 minutes, the temperature condition is 25-80 ℃, and the stirring speed is 100-3000 r/min;
the filtration in the step 4) is constant pressure filtration or reduced pressure filtration, and the washing solvent is one or more of deionized water, absolute ethyl alcohol, ethanol, diethyl ether, toluene, petroleum ether, dichloromethane, methanol and the like.
The SiO2The modified phase-change microcapsule is used in the fields of construction industry, textile field, military field, solar energy storage and the like.
Compared with the prior art, the invention has the beneficial effects that:
microcapsule technology effectively solvesThe encapsulation problem of the core material, but most phase-change microcapsules have the problems of low coating rate, easy leakage of the core material, easy damage of the capsules, low latent heat and the like, so that the phase-change microcapsules have poor heat storage capacity in practical addition application, and the latent heat of the phase-change material is difficult to be utilized to the maximum extent; the conventional solution is to increase the proportion of phase-change microcapsules in the composite material, but the excessive increase of the proportion of the phase-change microcapsules can affect the original performance of the composite material, and meanwhile, the cost is increased; the invention prepares SiO by2The modified phase-change microcapsule wall material can effectively improve the heat storage performance, the wrapping rate and the phase-change latent heat of the phase-change microcapsule, and further better exert the heat storage capacity in practical application.
Drawings
FIG. 1 shows SiO obtained in example 12Scanning electron microscopy of modified phase change microcapsules
FIG. 2 is a scanning electron microscope photograph of the phase-change microcapsules obtained in example 3
Detailed Description
The invention is further illustrated by the following examples and figures in the specification:
example 1
1. 3.0g of melamine, 8mL of 37% by mass aqueous formaldehyde solution and 0.09g of SiO were weighed2Adding the mixture into 20mL of deionized water, adjusting the pH value of the mixed solution to 8-9 by using triethanolamine, stirring the mixture in a constant-temperature water bath kettle at the temperature of 70 ℃ for reaction, wherein the stirring speed is 600r/min, and continuing stirring the mixture for reaction for 30min after the mixed solution is clarified to obtain SiO2Modified melamine resin prepolymer solution;
2. weighing 1.15g of styrene-maleic anhydride copolymer and 0.9g of sodium hydroxide, dissolving in 175mL of deionized water, and adjusting the pH of the mixed solution to 4-5 by using citric acid; adding 17.5g of paraffin into the mixed solution, fully melting the paraffin in a water bath at 70 ℃, stirring at the speed of 3000r/min for 60min, and ultrasonically dispersing for 10min by using ultrasonic waves after stirring to obtain the paraffin emulsion.
3. Placing the paraffin emulsion in 70 deg.C water bath, maintaining stirring speed of 600rpm/min, and dripping melamine resin prepolymer solution at 3.0mL/minEntering; the reaction temperature is maintained at 70 ℃, the stirring reaction is carried out for 2h, and the stirring speed is adjusted to 450 rpm/min. The reaction solution was adjusted to pH 9 with a 10 wt% aqueous solution of triethanolamine, and the reaction was terminated to obtain SiO2Modified phase change microcapsule materials.
4. Mixing SiO2The modified phase-change microcapsule material is filtered in a filtering device, washed for a plurality of times by deionized water at 50 ℃, and the filter cake after filtering and washing is put into a vacuum drying oven at 50 ℃ for drying for 48 hours to obtain SiO2Modified phase-change microcapsule powder.
SiO obtained in this example2The modified phase-change microcapsule is spherical, the particle size is 30-50um, the phase-change temperature is 31.76 ℃, and the phase-change latent heat is 142.4 kJ/kg.
Example 2
1. 3.0g of melamine, 8mL of 37% formaldehyde aqueous solution and 0.03g of SiO were weighed2Adding the mixture into 20mL of deionized water, adjusting the pH value of the mixed solution to 8-9 by using triethanolamine, stirring the mixture in a constant-temperature water bath kettle at the temperature of 70 ℃ for reaction, wherein the stirring speed is 600r/min, and continuing stirring the mixture for reaction for 30min after the mixed solution is clarified to obtain SiO2Modified melamine resin prepolymer solution;
2. weighing 1.15g of styrene-maleic anhydride copolymer and 0.9g of sodium hydroxide, dissolving in 175mL of deionized water, and adjusting the pH of the mixed solution to 4-5 by using citric acid; adding 17.5g of paraffin into the mixed solution, fully melting the paraffin in a water bath at 70 ℃, stirring at the speed of 3000r/min for 60min, and ultrasonically dispersing for 10min by using ultrasonic waves after stirring to obtain the paraffin emulsion.
3. Placing the paraffin emulsion in a water bath at 70 ℃, keeping the stirring speed of 600rpm/min, and dripping the melamine resin prepolymer solution at the speed of 3.0 mL/min; the reaction temperature is maintained at 70 ℃, the stirring reaction is carried out for 2h, and the stirring speed is adjusted to 450 rpm/min. The reaction solution was adjusted to pH 9 with a 10 wt% aqueous solution of triethanolamine, and the reaction was terminated to obtain SiO2Modified phase change microcapsule materials.
4. Mixing SiO2Suction filtering the modified phase-change microcapsule material in suction filtering equipment, washing with 50 deg.C deionized water for several times, and adding the filter cake after suction filtering and washing into 50Drying in a vacuum drying oven at the temperature of 48 hours to obtain SiO2Modified phase-change microcapsule powder.
SiO obtained in this example2The modified phase-change microcapsule is spherical, the particle size is 40-90um, the phase-change temperature is 28.45 ℃, and the phase-change latent heat is 130.6 kJ/kg.
Example 3
1. Weighing 3.0g of melamine and 8mL of formaldehyde aqueous solution with the mass fraction of 37%, adding the melamine and the formaldehyde aqueous solution into 20mL of deionized water, adjusting the pH value of the mixed solution to 8-9 by using triethanolamine, stirring the mixed solution in a constant-temperature water bath kettle at the temperature of 70 ℃ for reaction, wherein the stirring speed is 600r/min, and continuing stirring the mixed solution for reaction for 30min after the mixed solution is clarified to obtain melamine resin prepolymer solution;
2. weighing 1.15g of styrene-maleic anhydride copolymer and 0.9g of sodium hydroxide, dissolving in 175mL of deionized water, and adjusting the pH of the mixed solution to 4-5 by using citric acid; adding 17.5g of paraffin into the mixed solution, fully melting the paraffin in a water bath at 70 ℃, stirring at the speed of 3000r/min for 60min, and ultrasonically dispersing for 10min by using ultrasonic waves after stirring to obtain the paraffin emulsion.
3. Placing the paraffin emulsion in a water bath at 70 ℃, keeping the stirring speed of 600rpm/min, and dripping the melamine resin prepolymer solution at the speed of 3.0 mL/min; the reaction temperature is maintained at 70 ℃, the stirring reaction is carried out for 2h, and the stirring speed is adjusted to 450 rpm/min. The reaction solution was adjusted to pH 9 with a 10 wt% aqueous solution of triethanolamine, and the reaction was terminated to obtain a phase change microcapsule material.
4. Mixing SiO2And (3) carrying out suction filtration on the modified phase-change microcapsule material in suction filtration equipment, washing the modified phase-change microcapsule material for several times by using deionized water at 50 ℃, and drying a filter cake obtained after suction filtration and washing in a vacuum drying oven at 50 ℃ for 48 hours to obtain phase-change microcapsule powder.
The phase-change microcapsule obtained in the embodiment is spherical, the particle size is 20-50um, the phase-change temperature is 28.75 ℃, and the latent heat of phase change is 128.3 kJ/kg.
The above examples are only preferred embodiments of the present invention, it should be noted that: it will be apparent to those skilled in the art that various modifications and equivalents can be made without departing from the spirit of the invention, and it is intended that all such modifications and equivalents fall within the scope of the invention as defined in the claims.
Claims (11)
1. SiO (silicon dioxide)2The modified phase-change microcapsule is characterized by having a core-shell structure, wherein the shell (wall material) is melamine resin, the core (core material) is a phase-change material, and the modifier is SiO2。
2. SiO according to claim 12Modified phase change microcapsules, characterized in that the size of the phase change microcapsules is between 1nm and 500 μm.
3. SiO according to claims 1, 22The modified phase-change microcapsule is characterized in that the phase-change material (core material) accounts for 1-99% of the mass of the whole phase-change microcapsule.
4. SiO (silicon dioxide)2The preparation method of the modified phase-change microcapsule is characterized by comprising the following steps:
1) deionized water and SiO2Stirring and mixing the formaldehyde solution, the melamine and the triethanolamine under an alkaline condition; to obtain SiO2Modified melamine resin prepolymer;
2) dispersing and emulsifying deionized water, a phase-change material and an emulsifier under an acidic condition to obtain an emulsion.
3) Slowly dripping the prepolymer obtained in the step 1) into the emulsion obtained in the step 2), stirring the emulsion simultaneously until the prepolymer is completely dripped into the emulsion, continuously stirring for 2 hours, and adjusting the mixed solution to be in an alkaline state to obtain SiO2A modified phase change microcapsule slurry;
4) filtering, washing and drying to obtain SiO2Modified phase change microcapsules.
5. The method according to claim 4, wherein the dispersing and mixing time in the step 1) is 10 to 100 minutes, the temperature is 25 to 80 ℃, and the stirring speed is 100 to 3000 revolutions per minute.
6. The method according to claim 4, wherein the emulsification time in step 2) is 10 to 150 minutes, the temperature is 25 to 80 ℃, and the stirring speed is 100 to 20000 revolutions per minute.
7. The method according to claim 4, wherein the stirring time in the step 3) is 10 to 300 minutes, the temperature is 25 to 80 ℃, and the stirring speed is 100 to 3000 revolutions per minute.
8. The method according to claim 4, wherein the filtration in step 4) is a constant pressure filtration or a reduced pressure filtration, and the washing solvent is one or more selected from deionized water, absolute ethanol, diethyl ether, toluene, petroleum ether, dichloromethane, methanol, etc.
9. The SiO2The modified phase-change microcapsule is used in the fields of construction industry, textile industry, military field, solar energy storage and the like.
10. The phase-change material is paraffin, fatty acid, tetradecanol, hexadecanol or polyethylene glycol.
11. The emulsifier is one or more than two of styrene-maleic anhydride copolymer, sodium dodecyl benzene sulfonate and polyoxyethylene octyl phenol ether-10.
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| CN117304881A (en) * | 2023-09-26 | 2023-12-29 | 波司登羽绒服装有限公司 | Phase-change microcapsule material and preparation method and application thereof |
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