CN111821926A - Preparation method of melamine phase change microcapsule with low formaldehyde content - Google Patents
Preparation method of melamine phase change microcapsule with low formaldehyde content Download PDFInfo
- Publication number
- CN111821926A CN111821926A CN202010710563.5A CN202010710563A CN111821926A CN 111821926 A CN111821926 A CN 111821926A CN 202010710563 A CN202010710563 A CN 202010710563A CN 111821926 A CN111821926 A CN 111821926A
- Authority
- CN
- China
- Prior art keywords
- melamine
- solution
- stirring
- phase
- dropwise adding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a preparation method of a melamine phase-change microcapsule with low formaldehyde content, which comprises the steps of preparation of a prepolymer solution, preparation of an emulsion and coating reaction, wherein in the reaction of the prepolymer solution, melamine is fed, so that the reaction degree of the melamine and the formaldehyde is increased, the formaldehyde residue is reduced, in the coating reaction, the formaldehyde content of the middle section and the tail section of the reaction is lower through the use of an aldehyde eliminating agent, the free formaldehyde content of the obtained melamine phase-change microcapsule is far lower than that of the commercial product, and meanwhile, the obtained melamine phase-change microcapsule has good mechanical strength and thermal stability and can be applied to different fields.
Description
Technical Field
The invention relates to the technical field of phase-change materials, in particular to a preparation method of a melamine phase-change microcapsule with low formaldehyde content.
Background
The microcapsule technology is a technology for coating some functional substances by using organic or inorganic shells, and is widely applied to the fields of medicine, prevention, construction, electronics and the like at present. The phase change microcapsule technology is characterized in that a conventional box-type phase change material is subjected to micro-spheroidization, and an organic or inorganic shell material is coated outside the conventional box-type phase change material, so that the condition that the phase change material becomes liquid after phase change and cannot be normally used is avoided, the solid-liquid phase change process of the box-type phase change material is changed into solid-solid phase change macroscopically, the use convenience of the phase change material is greatly improved, the phase change material is safer and more stable, and the phase change material can be processed and used in many occasions.
Most of shell materials of phase change microcapsule products on the market at present are organic high molecular polymers, such as melamine resin, urea resin, PMMA (polymethyl methacrylate), polyurethane and the like, wherein the melamine resin microcapsules have obvious advantages in the aspects of shell strength, compactness, high temperature resistance, corrosion resistance and production stability compared with other types of materials, but because a formaldehyde solution is used as a raw material, if a production process and a post-treatment mode are improper, serious formaldehyde residues are generated, and the application of the formaldehyde solution in different fields is limited.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a melamine phase change microcapsule, which can reduce formaldehyde residue and has good strength performance.
The technical scheme of the invention is realized as follows: the invention provides a preparation method of melamine phase change microcapsules with low formaldehyde content, which comprises the following steps:
step one, mixing melamine, a standard formaldehyde solution and deionized water, and then dropwise adding triethanolamine to adjust the pH value of a system to 7.0-8.0 to obtain a first mixed solution;
step two, stirring the first mixed solution, heating to 70-80 ℃, keeping the stirring speed at 300-500rpm, adding melamine and continuing stirring when the solution is clear, stirring again until the solution is clear, adding the melamine and stirring again, stirring until the solution is clear, standing and preserving heat for 1 +/-0.5 h to obtain a prepolymer solution;
step three, adding the emulsifier and sodium dodecyl benzene sulfonate into deionized water, heating to 40-60 ℃, and stirring for 10-60min under the condition of heat preservation to obtain an emulsifier solution;
step four, heating and melting the phase change core material, then dropwise adding the phase change core material into the emulsifier solution obtained in the step three, heating the system to 70-80 ℃, and putting the system into a shearing emulsifier for emulsification, wherein the rotating speed of the shearing emulsifier is 8000-15000rpm, and the emulsifying time is 1 +/-0.5 h, so as to obtain an emulsion after the emulsification;
and step five, heating the emulsion obtained in the step four to 70-80 ℃, keeping the rotation speed at 400-one-time stirring at 600rpm, dropwise adding an acetic acid solution in the stirring process to adjust the pH value of the system to 3.0-5.0, dropwise adding the prepolymer solution obtained in the step two into a flask to perform a coating reaction to obtain a reaction solution, wherein the dropwise adding time is 1-2h, adding a first aldehyde eliminating agent in the dropwise adding process, keeping the temperature for 10-60min after the dropwise adding is finished, dropwise adding a triethanolamine solution to adjust the pH value of the system to 8.0-10.0, adding a second aldehyde eliminating agent after the adjustment is finished, keeping stirring for 10min, cooling to normal temperature, and discharging to obtain the low-formaldehyde-content melamine phase-change microcapsule suspension.
On the basis of the technical scheme, preferably, the melamine phase change microcapsule suspension obtained in the fifth step is filtered and dried to obtain the melamine phase change microcapsule with low formaldehyde content.
On the basis of the above technical solution, preferably, in the step one, the melamine is: standard formaldehyde solution: deionized water is 1: (4-5): (4-5).
On the basis of the technical scheme, preferably, the mass ratio of the melamine added in the step one to the melamine added for the first time and the melamine added for the second time in the step two is 1: (0.6-1): (0.6-1).
On the basis of the technical scheme, preferably, the mass ratio of the melamine to the emulsifier, the sodium dodecyl benzene sulfonate and the deionized water in the step one is 1: (0.16-0.34): (0.16-0.34): (30-70).
On the basis of the technical scheme, preferably, the dosage of the emulsifier is the same as that of the sodium dodecyl benzene sulfonate.
More preferably, the mass ratio of the melamine in the first step to the phase-change core material in the fourth step is 1: (10-20).
On the basis of the above technical scheme, preferably, in the fifth step, the dosage of the first aldehyde eliminating agent is 0.1-1% of the mass of the reaction liquid, and the dosage of the second aldehyde eliminating agent is 0.1-1% of the mass of the reaction liquid.
On the basis of the technical scheme, preferably, the mass concentration of the triethanolamine is 8-12%, and the mass concentration of the acetic acid solution is 8-12%.
On the basis of the technical scheme, preferably, the emulsifier is one of triton, OP-10, nonylphenol polyvinyl ether or sodium alkylsulfate.
On the basis of the technical scheme, preferably, the phase change core material is C20A normal alkane.
On the basis of the above technical solution, preferably, C is20The purity of the normal alkane is not less than 90%, and preferably, the C20The purity of the normal alkane is more than 99 percent.
On the basis of the technical scheme, preferably, the first aldehyde eliminating agent and the second aldehyde eliminating agent are one or a mixture of more of urea, a polyphenol compound, acetyl ethylamine, cysteine hydrochloride and tannin.
Compared with the prior art, the preparation method of the melamine phase change microcapsule with low formaldehyde content has the following beneficial effects:
(1) in the preparation process of the prepolymer solution, the melamine is fed for many times, so that the reaction degree of the melamine and the formaldehyde is increased, the formed prepolymer monomer has less residue, the reaction degree of the formaldehyde in a small amount of the prepolymer solution is increased, the formed prepolymer monomer has less residue, the content of the formaldehyde in the prepolymer solution is reduced, the toughness of the microcapsule involucra is improved, the microcapsule involucra is not easy to break, and the strength performance of the microcapsule involucra is enhanced;
(2) the formaldehyde eliminating agent is added into the reaction liquid, so that the free formaldehyde in the system is eliminated and controlled in the middle process and the end process of the reaction, the content of the formaldehyde in the final finished product is reduced to the maximum extent, and the formaldehyde eliminating agent can be better applied to different technical fields.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
30g of melamine, 120g of 36% mass concentration standard formaldehyde solution and 120g of deionized water are weighed, added into a beaker for mixing, and 8% mass concentration triethanolamine is added dropwise to adjust the pH value to 8.0, so that the first mixed solution is in a slightly alkaline environment, and 271g of first mixed solution is obtained.
And (2) putting the first mixed solution into a stirrer to be stirred at the stirring speed of 300rpm, simultaneously heating to 70 ℃ to perform prepolymer reaction, stirring until the solution is in a clear state, adding 18g of melamine and continuing stirring, after stirring to be in the clear state, adding 18g of melamine again, keeping stirring until the solution is clear, stopping stirring, standing at 70 ℃ and performing heat preservation reaction for 0.5h to obtain 307g of prepolymer solution.
Adding 4.8g of triton and 4.8g of sodium dodecyl benzene sulfonate into 900ml of deionized water, heating to 40 ℃, and stirring for 10min under the condition of heat preservation to obtain 910g of emulsified solution.
300g of C with a purity of 80%20Heating n-alkane to a molten state, dropwise adding the n-alkane into the emulsified solution, keeping the temperature of the system at 70 ℃, putting the system into a shearing emulsifier for emulsification, and shearing and stirring the shearing emulsifier at the rotation speed of 8000rpm for 0.5h to obtain 1210g of emulsion after emulsification.
Heating the emulsion to 70 ℃, keeping the rotation speed at 400rpm, stirring, dropwise adding 8% acetic acid solution in the stirring process to adjust the pH value of the system to 3.0, dropwise adding the prepolymer solution into a flask to perform a coating reaction to obtain 1520g of reaction liquid, wherein the dropwise adding time is 1h, adding 1.5g of urea in the dropwise adding process, preserving heat for 10min after the dropwise adding is finished, dropwise adding triethanolamine solution to adjust the pH value of the system to 8.0, adjusting, adding 1.5g of catechin, stirring for 10min, cooling to normal temperature, and discharging to obtain the low-formaldehyde-content melamine phase-change microcapsule suspension.
Example 2
30g of melamine, 150g of 37% mass concentration standard formaldehyde solution and 150g of deionized water are weighed, added into a beaker for mixing, and 12% mass concentration triethanolamine is added dropwise to adjust the pH value to 8.0, so that the mixture is in a slightly alkaline environment, and 331g of first mixed solution is obtained.
And (2) putting the first mixed solution into a stirrer to be stirred at the speed of 500rpm, simultaneously heating to 80 ℃ to perform prepolymer reaction, stirring until the solution is in a clear state, adding 30g of melamine and continuing stirring, after stirring to be in the clear state, adding 30g of melamine again, keeping stirring until the solution is clear, stopping stirring, standing at 80 ℃ and performing heat preservation reaction for 1.5 hours to obtain 391g of prepolymer solution.
10gOP-10 g and 10g sodium dodecyl benzene sulfonate are added into 2100ml deionized water, heated to 60 ℃, kept warm and stirred for 60min to obtain 2120g of emulsified solution.
600g of C with a purity of 99%20Heating n-alkane to a molten state, dropwise adding the n-alkane into the emulsified solution, keeping the temperature of the system at 80 ℃, putting the system into a shearing emulsifier for emulsification, and shearing and stirring the shearing emulsifier at the rotating speed of 15000rpm for 1.5 hours to obtain 2720g of emulsified liquid after emulsification.
Heating the emulsion to 80 ℃, keeping the rotation speed at 600rpm, stirring, dropwise adding 12% acetic acid solution in the stirring process to adjust the pH value of the system to 5.0, dropwise adding the prepolymer solution into the flask to perform a coating reaction to obtain a reaction solution, wherein the dropwise adding time is 2 hours, adding 31.1g of acetoacetamine in the dropwise adding process, preserving the temperature for 60min after the dropwise adding is finished, dropwise adding triethanolamine solution to adjust the pH value of the system to 10.0, adjusting, adding 31.1g of cysteine hydrochloride, stirring for 10min, cooling to normal temperature, and discharging to obtain the melamine phase change microcapsule suspension with low formaldehyde content.
Example 3
30g of melamine, 130g of 38% mass concentration standard formaldehyde solution and 130g of deionized water are weighed and added into a beaker for mixing, 10% mass concentration triethanolamine is added dropwise to adjust the pH value to 7.5, so that the mixture is in a slightly alkaline environment, and 292g of first mixed solution is obtained.
And (2) putting the first mixed solution into a stirrer to be stirred at the stirring speed of 400rpm, simultaneously heating to 75 ℃ to perform prepolymer reaction, stirring until the solution is in a clear state, adding 21g of melamine and continuing stirring, after stirring to be in the clear state, adding 21g of melamine again, keeping stirring until the solution is clear, stopping stirring, standing at 75 ℃ and performing heat preservation reaction for 1h to obtain 334g of prepolymer solution.
Adding 6g of nonylphenol polyvinyl ether and 6g of sodium dodecyl benzene sulfonate into 1200ml of deionized water, heating to 40-60 ℃, and stirring for 30min under the condition of heat preservation to obtain 1212g of emulsified solution.
450g of C with a purity of 90%20Heating n-alkane to a molten state, dropwise adding the n-alkane into the emulsified solution, keeping the temperature of the system at 75 ℃, putting the system into a shearing emulsifier for emulsification, and shearing and stirring the shearing emulsifier at the rotation speed of 10000rpm for 1h to obtain 1662g of emulsified liquid after emulsification.
Heating the emulsion to 75 ℃, keeping the rotation speed at 500rpm, stirring, dropwise adding 10% acetic acid solution in the stirring process to adjust the pH value of the system to be 4.0, dropwise adding the prepolymer solution into a flask to perform a coating reaction to obtain a reaction solution 2000, wherein the dropwise adding time is 1-2h, adding 5g of urea and 5g of tannin in the dropwise adding process, preserving the temperature for 30min after the dropwise adding is finished, dropwise adding triethanolamine solution to adjust the pH value of the system to be 9.0, adjusting, adding 10g of cysteine hydrochloride, stirring for 10min, cooling to normal temperature, and discharging to obtain the melamine phase change microcapsule suspension with low formaldehyde content.
Example 4
30g of melamine, 140g of 37% mass concentration standard formaldehyde solution and 140g of deionized water are weighed, added into a beaker for mixing, and 10% mass concentration triethanolamine is added dropwise to adjust the pH value to 7.2, so that the first mixed solution is in a slightly alkaline environment, and 312g of first mixed solution is obtained.
And (2) putting the first mixed solution into a stirrer to be stirred at the stirring speed of 400rpm, simultaneously heating to 72 ℃ to perform prepolymer reaction, stirring until the solution is in a clear state, adding 24g of melamine and continuing stirring, after stirring to be in the clear state, adding 24g of melamine again, keeping stirring until the solution is clear, stopping stirring, standing at 72 ℃ for heat preservation reaction for 1h, and obtaining 360g of prepolymer solution.
Adding 7.5g of sodium dodecyl sulfate and 7.5g of sodium dodecyl benzene sulfonate into 1500ml of deionized water, heating to 55 ℃, and stirring for 40min under the condition of heat preservation to obtain 1515g of emulsified solution.
360g of C with a purity of 99%20Heating n-alkane to a molten state, dropwise adding the n-alkane into the emulsified solution, keeping the temperature of the system at 72 ℃, putting the system into a shearing emulsifier for emulsification, and shearing and stirring the shearing emulsifier at the rotating speed of 12000rpm for 1h to obtain 1875g of emulsified liquid after the emulsification is finished.
Heating the emulsion to 72 ℃, keeping the rotation speed at 600rpm, stirring, dropwise adding 10% acetic acid solution in the stirring process to adjust the pH value of the system to 4.2, dropwise adding the prepolymer solution into a flask to perform a coating reaction to obtain a reaction solution, wherein the dropwise adding time is 1.5h, adding 11g of cysteine hydrochloride in the dropwise adding process, keeping the temperature for 50min after the dropwise adding is finished, dropwise adding triethanolamine solution to adjust the pH value of the system to 9.0, adding 11g of catechin after the adjustment is finished, stirring for 10min, cooling to normal temperature, and discharging to obtain the low-formaldehyde-content melamine phase-change microcapsule suspension.
Example 5
30g of melamine, 136g of 36% mass concentration standard formaldehyde solution and 140g of deionized water are weighed, added into a beaker for mixing, and 10% mass concentration triethanolamine is added dropwise to adjust the pH value to 7.4, so that the mixture is in a slightly alkaline environment, and 310g of first mixed solution is obtained.
And (2) putting the first mixed solution into a stirrer to be stirred at the stirring speed of 500rpm, simultaneously heating to 78 ℃ to perform prepolymer reaction, stirring until the solution is in a clear state, adding 27g of melamine and continuing stirring, after stirring to be in the clear state, adding 27g of melamine again, keeping stirring until the solution is clear, stopping stirring, standing at 70-80 ℃ for heat preservation reaction for 0.5-1.5h, and obtaining 364g of prepolymer solution.
9g of nonylphenol polyoxyethylene ether and 9g of sodium dodecyl benzene sulfonate are added into 1800ml of deionized water, heated to 55 ℃, kept warm and stirred for 50min to obtain 1818g of an emulsified solution.
540g of C with a purity of 99 percent20Heating n-alkane to a molten state, dropwise adding the n-alkane into the emulsified solution, keeping the temperature of the system at 78 ℃, putting the system into a shearing emulsifier for emulsification, and shearing and stirring the shearing emulsifier at the rotating speed of 15000rpm for 1.2 hours to obtain 2358g of emulsified liquid after emulsification.
Heating the emulsion to 78 ℃, keeping the rotation speed at 600rpm, stirring, dropwise adding 10% acetic acid solution in the stirring process to adjust the pH value of the system to 4.2, dropwise adding the prepolymer solution into a flask to perform a coating reaction to obtain 2722g of reaction liquid, wherein the dropwise adding time is 1h, adding 25g of catechin in the dropwise adding process, preserving heat for 60min after the dropwise adding is finished, dropwise adding triethanolamine solution to adjust the pH value of the system to 10.0, adjusting, adding 15g of urea and 10g of acetoacetamine, stirring for 10min, cooling to normal temperature, and discharging to obtain the low-formaldehyde-content melamine phase-change microcapsule suspension.
Experiment one: formaldehyde residue detection for melamine phase change microcapsules
The experimental method comprises the following steps: taking the melamine phase-change microcapsule suspension with low formaldehyde content prepared in the embodiment 1-5, carrying out suction filtration, taking the filtrate, detecting the formaldehyde content in the filtrate by adopting a spectrophotometry, wherein the detection result is as follows:
| grouping | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Content of Formaldehyde | 1ppm | 1ppm | 2ppm | 1ppm | 1ppm |
As can be seen, the melamine phase-change microcapsule suspension prepared by the preparation method has little formaldehyde residue.
Experiment two: detection of thermal stability and mechanical strength of melamine phase change microcapsules
The experimental method comprises the following steps: respectively carrying out suction filtration and drying on the melamine phase change microcapsule turbid liquids with low formaldehyde content prepared in the embodiments 1-5 to obtain phase change microcapsules, placing the same amount of phase change microcapsules into a high-pressure kettle, standing for 10min under the conditions of 150 ℃ and 10MPa, simultaneously carrying out test comparison by taking a certain commercially available melamine phase change microcapsule as a comparative example, observing whether the phase change material leaks from the inner wall of the high-pressure kettle, and grading according to the leakage condition, wherein the full score is 10 minutes, if the inner wall of the high-pressure kettle is smooth and has no phase change material leakage, the full score is 10 minutes, and the more leakage and the lower score are sequentially graded according to the leakage amount. The specific scores were as follows:
| grouping | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| Scoring | 8 | 9 | 10 | 10 | 9 | 3 |
The mechanical strength and the thermal stability of the melamine phase-change microcapsule prepared by the preparation method are far stronger than those of the melamine phase-change microcapsule sold in the market, and the melamine phase-change microcapsule can be better applied to different fields.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of melamine phase change microcapsules with low formaldehyde content is characterized by comprising the following steps:
step one, mixing melamine, a standard formaldehyde solution and deionized water, and then dropwise adding triethanolamine to adjust the pH value of a system to 7.0-8.0 to obtain a first mixed solution;
step two, stirring the first mixed solution, heating to 70-80 ℃, keeping the stirring speed at 300-500rpm, adding melamine and continuing stirring when the solution is clear, stirring again until the solution is clear, adding the melamine and stirring again, stirring until the solution is clear, standing and preserving heat for 1 +/-0.5 h to obtain a prepolymer solution;
step three, adding the emulsifier and sodium dodecyl benzene sulfonate into deionized water, heating to 40-60 ℃, and stirring for 10-60min under the condition of heat preservation to obtain an emulsifier solution;
step four, heating and melting the phase change core material, then dropwise adding the phase change core material into the emulsifier solution obtained in the step three, heating the system to 70-80 ℃, and putting the system into a shearing emulsifier for emulsification, wherein the rotating speed of the shearing emulsifier is 8000-15000rpm, and the emulsifying time is 1 +/-0.5 h, so as to obtain an emulsion after the emulsification;
and step five, heating the emulsion obtained in the step four to 70-80 ℃, keeping the rotation speed at 400-one-time stirring at 600rpm, dropwise adding an acetic acid solution in the stirring process to adjust the pH value of the system to 3.0-5.0, dropwise adding the prepolymer solution obtained in the step two into a flask to perform a coating reaction to obtain a reaction solution, wherein the dropwise adding time is 1-2h, adding a first aldehyde eliminating agent in the dropwise adding process, keeping the temperature for 10-60min after the dropwise adding is finished, dropwise adding a triethanolamine solution to adjust the pH value of the system to 8.0-10.0, adding a second aldehyde eliminating agent after the adjustment is finished, keeping stirring for 10min, cooling to normal temperature, and discharging to obtain the low-formaldehyde-content melamine phase-change microcapsule suspension.
2. The method for preparing melamine phase-change microcapsules with low formaldehyde content according to claim 1, wherein in step one, the weight ratio of melamine: standard formaldehyde solution: deionized water is 1: (4-5): (4-5).
3. The method for preparing the melamine phase-change microcapsule with low formaldehyde content according to claim 2, wherein the mass ratio of the melamine added in the first step to the melamine added in the first step and the melamine added in the second step is 1: (0.6-1): (0.6-1).
4. The method for preparing the melamine phase-change microcapsule with low formaldehyde content according to claim 2, wherein the mass ratio of the melamine in the first step to the emulsifier, the sodium dodecyl benzene sulfonate and the deionized water in the third step is 1: (0.16-0.34): (0.16-0.34): (30-70).
5. The preparation method of the melamine phase-change microcapsule with low formaldehyde content as claimed in claim 2, wherein the mass ratio of the melamine in the first step to the phase-change core material in the fourth step is 1: (10-20).
6. The method for preparing melamine phase-change microcapsules with low formaldehyde content as claimed in claim 5, wherein in step five, the amount of the first aldehyde eliminating agent is 0.1-1% of the mass of the reaction solution, and the amount of the second aldehyde eliminating agent is 0.1-1% of the mass of the reaction solution.
7. The method for preparing melamine phase-change microcapsules with low formaldehyde content according to claim 1, wherein the triethanolamine has a mass concentration of 8-12% and the acetic acid solution has a mass concentration of 8-12%.
8. The method for preparing melamine phase change microcapsules with low formaldehyde content as claimed in claim 1, wherein the emulsifier is one of triton, OP-10, nonylphenol polyvinyl ether or sodium alkylsulfate.
9. The method for preparing melamine phase-change microcapsules with low formaldehyde content according to claim 1, wherein the phase-change core material is C20A normal alkane.
10. The method for preparing the melamine phase-change microcapsule with low formaldehyde content as claimed in claim 1, wherein the first aldehyde-eliminating agent and the second aldehyde-eliminating agent are both one or a mixture of more of urea, polyphenol compounds, acetyl ethylamine, cysteine hydrochloride and tannin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010710563.5A CN111821926B (en) | 2020-07-22 | 2020-07-22 | Preparation method of melamine phase change microcapsule with low formaldehyde content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010710563.5A CN111821926B (en) | 2020-07-22 | 2020-07-22 | Preparation method of melamine phase change microcapsule with low formaldehyde content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111821926A true CN111821926A (en) | 2020-10-27 |
| CN111821926B CN111821926B (en) | 2022-08-09 |
Family
ID=72924696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010710563.5A Active CN111821926B (en) | 2020-07-22 | 2020-07-22 | Preparation method of melamine phase change microcapsule with low formaldehyde content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111821926B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113797860A (en) * | 2021-09-13 | 2021-12-17 | 武汉中科先进技术研究院有限公司 | Preparation of melamine resin phase change microcapsule with low supercooling degree and low formaldehyde |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6224795B1 (en) * | 1998-07-24 | 2001-05-01 | Basf Aktiengesellschaft | Low-formaldehyde dispersion of microcapsules of melamine-formaldehyde resins |
| US20030004226A1 (en) * | 2000-01-10 | 2003-01-02 | Dietrich Hoffman | Low-viscosity, melamine-formaldehyde resin microcapsule dispersions with reduced formaldehyde content |
| CN101113322A (en) * | 2006-07-24 | 2008-01-30 | 中国科学院化学研究所 | Method for preparation of monodisperse phase-change microcapsule |
| US20100087115A1 (en) * | 2008-10-08 | 2010-04-08 | Microtek Laboratories, Inc. | Microencapsulation of a phase change material with enhanced flame resistance |
| US20100237520A1 (en) * | 2007-08-31 | 2010-09-23 | Korea Research Institute Of Chemical Technology | Preparation of microcapsule with double layered structure |
| CN102746826A (en) * | 2012-06-06 | 2012-10-24 | 天津工业大学 | Diol composite fatty alcohol energy storage microcapsule and preparation method thereof |
| CN103537238A (en) * | 2013-09-26 | 2014-01-29 | 航天海鹰(镇江)特种材料有限公司 | Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule |
| CN104861935A (en) * | 2015-05-26 | 2015-08-26 | 西南科技大学 | Preparation method of phase change microcapsule |
| US20170065956A1 (en) * | 2015-08-18 | 2017-03-09 | Microtek Laboratories, Inc. | Methods for making low remnant free formaldehyde microcapsules and microcapsules made by same |
| US20180215983A1 (en) * | 2017-01-27 | 2018-08-02 | Encapsys, Llc | Encapsulates |
| CN108854878A (en) * | 2018-06-28 | 2018-11-23 | 南昌大学 | A kind of capric acid microcapsules and preparation method thereof |
| CN110343511A (en) * | 2019-07-31 | 2019-10-18 | 北京林业大学 | A kind of nano-zirconium carbide modified paraffin phase-change microcapsule and preparation method thereof |
| CN110368879A (en) * | 2019-07-18 | 2019-10-25 | 太原理工大学 | A kind of self-repairing microcapsule and preparation method thereof, selfreparing basalt fibre and preparation method thereof |
| CN110578258A (en) * | 2019-07-01 | 2019-12-17 | 绍兴墨织韵纺织科技有限公司 | Preparation process of photochromic polypropylene yarn fabric |
-
2020
- 2020-07-22 CN CN202010710563.5A patent/CN111821926B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6224795B1 (en) * | 1998-07-24 | 2001-05-01 | Basf Aktiengesellschaft | Low-formaldehyde dispersion of microcapsules of melamine-formaldehyde resins |
| US20030004226A1 (en) * | 2000-01-10 | 2003-01-02 | Dietrich Hoffman | Low-viscosity, melamine-formaldehyde resin microcapsule dispersions with reduced formaldehyde content |
| CN101113322A (en) * | 2006-07-24 | 2008-01-30 | 中国科学院化学研究所 | Method for preparation of monodisperse phase-change microcapsule |
| US20100237520A1 (en) * | 2007-08-31 | 2010-09-23 | Korea Research Institute Of Chemical Technology | Preparation of microcapsule with double layered structure |
| US20100087115A1 (en) * | 2008-10-08 | 2010-04-08 | Microtek Laboratories, Inc. | Microencapsulation of a phase change material with enhanced flame resistance |
| CN102746826A (en) * | 2012-06-06 | 2012-10-24 | 天津工业大学 | Diol composite fatty alcohol energy storage microcapsule and preparation method thereof |
| CN103537238A (en) * | 2013-09-26 | 2014-01-29 | 航天海鹰(镇江)特种材料有限公司 | Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule |
| CN104861935A (en) * | 2015-05-26 | 2015-08-26 | 西南科技大学 | Preparation method of phase change microcapsule |
| US20170065956A1 (en) * | 2015-08-18 | 2017-03-09 | Microtek Laboratories, Inc. | Methods for making low remnant free formaldehyde microcapsules and microcapsules made by same |
| US20180215983A1 (en) * | 2017-01-27 | 2018-08-02 | Encapsys, Llc | Encapsulates |
| CN108854878A (en) * | 2018-06-28 | 2018-11-23 | 南昌大学 | A kind of capric acid microcapsules and preparation method thereof |
| CN110578258A (en) * | 2019-07-01 | 2019-12-17 | 绍兴墨织韵纺织科技有限公司 | Preparation process of photochromic polypropylene yarn fabric |
| CN110368879A (en) * | 2019-07-18 | 2019-10-25 | 太原理工大学 | A kind of self-repairing microcapsule and preparation method thereof, selfreparing basalt fibre and preparation method thereof |
| CN110343511A (en) * | 2019-07-31 | 2019-10-18 | 北京林业大学 | A kind of nano-zirconium carbide modified paraffin phase-change microcapsule and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 仇中柱，李晟南: "相变微胶囊悬浮液中颗粒润湿性对导热系数的影响", 《材料导报》 * |
| 季佳: "《木材胶粘剂生产技术》", 30 June 2000, 化学工业出版社 * |
| 李伟, 张兴祥: "相变材料微胶囊的制备及提纯", 《高分子材料科学与工程》 * |
| 王先锋，赵涛: "预聚合条件对密胺树脂相变微胶囊包覆效率的影响", 《高分子材料科学与工程》 * |
| 马永祥: "《化学与生活》", 30 November 2017, 山东人民出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113797860A (en) * | 2021-09-13 | 2021-12-17 | 武汉中科先进技术研究院有限公司 | Preparation of melamine resin phase change microcapsule with low supercooling degree and low formaldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111821926B (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1444621C2 (en) | Process for the production of chromogen-bound polymers | |
| CN111821926B (en) | Preparation method of melamine phase change microcapsule with low formaldehyde content | |
| CN102806022B (en) | Method for preparing polyacrylonitrile (PAN)-base microporous membrane | |
| SU1222201A3 (en) | Compound for sizing paper | |
| US3872023A (en) | Microcapsules having walls made of copolymer of methylmethacrylate and acetylacetates of mono(meth) acrylates of aliphatic diols | |
| CN110760019B (en) | Vinyl chloride polymerization terminator, preparation method and application thereof | |
| US4135043A (en) | Process for preparing polymers in powder form | |
| NO145166B (en) | PROCEDURE FOR THE PREPARATION OF VINYL CHLORIDE POLYMERS WHICH CAN PREPARE | |
| US3041318A (en) | Process for recovering water soluble polymers | |
| US4110520A (en) | Modification of water-soluble acrylic polymer | |
| NO762283L (en) | ||
| CN101475730A (en) | Preparation of bilaminar membrane sulfur microcapsule | |
| US2422754A (en) | Preparation of polyvinyl acetal resins | |
| US10414879B2 (en) | Process to produce fluoropolymer-based latex with mechanical stability | |
| US4327004A (en) | Aqueous dispersions of plastics in which the average diameter of the dispersion particles is in the range from about 50 to 500 nm, and a process for their preparation | |
| AU612873B2 (en) | Method of preventing polymer scale formation | |
| CN106699936B (en) | A kind of preparation method of high molecular weight sodium polyacrylate | |
| US4965328A (en) | Preparation of paste forming vinyl chloride polymers with high pressure homogenization | |
| US2265937A (en) | Treatment of methacrylic acid esters | |
| CN114557342A (en) | Preparation method of fluopyram microcapsule suspending agent | |
| US3242146A (en) | Process for the production of condensation products | |
| SU383309A1 (en) | ||
| EP0030524B1 (en) | A method of polymerizing vinyl chloride | |
| US2357469A (en) | Isolation of water insoluble cellulose hydroxy fatty acids and their water soluble salts | |
| EP0072405B1 (en) | Process for the preparation of free-flowing, non adhesive vinyl chloride graft polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: No. 7 Tianyu Avenue, Xiangcheng High tech Development Zone, Xiangcheng District, Xiangyang City, Hubei Province, 441000 Patentee after: Hubei Aerospace Chemical New Materials Technology Co.,Ltd. Address before: 441000 No.2 Zhonghang Road, Aerospace Industrial Park, Dengcheng Avenue, Fancheng District, Xiangyang City, Hubei Province Patentee before: XIANGYANG SUNVAIOR AEROSPACE FILMS Co.,Ltd. |
|
| CP03 | Change of name, title or address |