WO2021012303A1 - Double-shell phase change microcapsule and preparation method therefor - Google Patents

Double-shell phase change microcapsule and preparation method therefor Download PDF

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WO2021012303A1
WO2021012303A1 PCT/CN2019/098600 CN2019098600W WO2021012303A1 WO 2021012303 A1 WO2021012303 A1 WO 2021012303A1 CN 2019098600 W CN2019098600 W CN 2019098600W WO 2021012303 A1 WO2021012303 A1 WO 2021012303A1
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phase change
double
shell
add
microcapsules
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PCT/CN2019/098600
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French (fr)
Chinese (zh)
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杨晶磊
安金亮
郭晔
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广州市香港科大***研究院
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • 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

Definitions

  • the invention relates to a double-shell phase change microcapsule and a preparation method thereof, and belongs to the technical field of microcapsule phase change materials.
  • Phase change material Material refers to a type of material that can absorb or release a large amount of energy (that is, the enthalpy of phase change) when a phase change occurs.
  • phase change materials There are many types of phase change materials, which can be classified according to different classification methods. For example, they can be divided into solid-solid phase change materials, solid-liquid phase change materials, and solid-gas phase change materials according to the phase change method; Inorganic phase change materials, organic phase change materials and composite phase change materials.
  • phase change material When a phase change material undergoes a phase change, it needs to absorb heat from the environment or release heat to the environment, and its physical state will also change.
  • the energy that can be stored or released when the physical state of a phase change material changes is called phase change heat.
  • Phase change materials can realize heat storage through phase transition and are an important latent heat storage material with good potential application prospects.
  • phase change material when the solid-liquid phase change material undergoes phase change, it has defects such as easy leakage, corrosiveness, unstable volume, easy phase separation, and poor heat transfer performance.
  • people encapsulate the phase change material.
  • the particle size of the capsule is micron or nanometer, it can not only increase the specific surface area and heat transfer area of the capsule, but also increase the heat storage/release rate of the capsule, thereby expanding
  • the application range of phase change materials for example, if the phase change materials are directly applied to buildings, there will be problems such as the extravasation of the phase change materials and the frosting on the surface of the building walls, and the phase change materials are prepared into micro/nano capsules and then used These problems do not arise when building materials.
  • phase change microcapsules generally use melamine, polyurea, polyurethane, polyurea-formaldehyde, etc. as the shell, and most of them are wrapped by a single type of shell material.
  • the shell has problems such as too hard or too soft, which leads to the shell Poor flexibility, poor high temperature resistance, poor thermal cycle performance and poor solvent resistance.
  • the single-layer shell has poor resistance to water and organic solvents and is prone to cracking. Therefore, the practical application of phase change microcapsules is greatly restricted.
  • the purpose of the present invention is to provide a double-shell phase change microcapsule and a preparation method thereof.
  • a two-layer shell phase change microcapsule is composed of a core material, an inner shell and an outer shell, the core material is a phase change material, and the inner shell is composed of polyurea or/and polyurethane, The outer shell is composed of polyurea-formaldehyde.
  • the phase change material is at least one of C 14 to C 34 linear alkanes and C 12 to C 34 long chain fatty acids.
  • the phase change material is at least one of paraffin, lauric acid, and octadecanoic acid.
  • the particle size of the phase change microcapsules is 0.5-500 ⁇ m, and the core material accounts for 20-80 wt%.
  • the preparation method of the above-mentioned double-shell phase change microcapsule includes the following steps:
  • the method for preparing the above-mentioned double-shell phase change microcapsules includes the following steps:
  • the mass ratio of the phase change material, isocyanate, polyol or/and polyamine, urea, formaldehyde, and polyphenol is 1:(0.025 ⁇ 0.250):(0.05 ⁇ 0.25):(0.05 ⁇ 0.50):( 0.05 ⁇ 1.00): (0.025 ⁇ 0.500).
  • the mass ratio of the phase change material and emulsifier in step 1) is 1: (0.015 to 0.150).
  • the emulsifier in step 1) is at least one of gum arabic, polyvinyl alcohol, and emulsifier OP-10.
  • the isocyanate in step 1) is at least one of HDI, MDI, IPDI, HDI dimer, and HDI trimer.
  • the polyol in step 2) is at least one of 1,4-dibutanol, 1,6-hexanediol, glycerol, sorbitol, and polyether polyol.
  • the polyamine is at least one of 1,6-hexanediamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine.
  • the mass fraction of the formaldehyde solution in step 3) is 37%-40%.
  • the mass ratio of the phase change material to the dispersant is 1: (0.025 to 0.500).
  • the dispersant in step 4) is at least one of ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and gum arabic.
  • the polyhydric phenol in step 4) is at least one of catechol, resorcinol, and hydroquinone.
  • the phase change microcapsules of the present invention have good high temperature resistance, cold and heat cycle resistance and solvent resistance, simple preparation process, low production cost, and can be widely used in construction, textile and clothing, electronics Products, military and other fields.
  • phase change microcapsules of the present invention will not volatilize until the temperature rises above 150°C, and the peak shape of the melting-solidification curve of the phase change microcapsules remains unchanged after 100 cycles of -5°C to 60°C.
  • the enthalpy of fusion remains basically unchanged, and the high temperature resistance and thermal cycle resistance are excellent;
  • phase change microcapsule of the present invention has a core material loss rate of only 6%-11% after continuous immersion in water, n-hexane, xylene, ethyl acetate and other solvents for 20 days, and has excellent solvent resistance.
  • FIG. 1 is an SEM image of the double-shell phase change microcapsule of Example 1.
  • Fig. 2 shows the melting-solidification curves of the double-shell phase change microcapsules of Example 1 after one and 100 heat and cold cycles.
  • FIG. 3 is a DSC chart of the double-shell phase change microcapsules of Example 1.
  • FIG. 4 is a TGA diagram of the double-shell phase change microcapsule of Example 1.
  • FIG. 5 is an SEM image of the double-shell phase change microcapsule of Example 2.
  • Example 6 is a DSC chart of the double-shell phase change microcapsules of Example 2.
  • Example 7 is a TGA diagram of the double-shell phase change microcapsule of Example 2.
  • FIG. 8 is an SEM image of the double-shell phase change microcapsule of Example 3.
  • FIG. 10 is an SEM image of the double-shell phase change microcapsule of Example 4.
  • FIG. 11 is a DSC chart of the double-shell phase change microcapsules of Example 4.
  • a method for preparing double-shell phase change microcapsules includes the following steps:
  • the particle size of the phase change microcapsules is 20-60 ⁇ m.
  • Figure 2 shows the melting-solidification curve of the double-shell phase change microcapsules after one time and 100 cycles of -5°C to 60°C.
  • phase change enthalpy of the phase change microcapsules is about 200J/g.
  • the core material content of the phase change microcapsules is about 73wt%, and the core material of the microcapsules does not start to lose until heated to about 150°C.
  • a method for preparing double-shell phase change microcapsules includes the following steps:
  • phase change microcapsules were controlled at a stirring speed of 400 rpm, stirred at a constant temperature of 58°C for 120 minutes, filtered, washed with water, and dried to obtain a double-shell phase change microcapsule.
  • the particle size of the phase change microcapsules is 40 to 90 ⁇ m.
  • Example 3 The same method as in Example 1 was used to test the solvent resistance of the double-shell phase-change microcapsules, and the double-shell phase-change microcapsules were soaked in water, n-hexane, xylene and ethyl acetate. After 20 days, the core material loss rate was 5.0%, 3.5%, 7.0% and 9.6% respectively.
  • phase change enthalpy of the phase change microcapsules is about 130 J/g.
  • the core material content of the phase change microcapsules is about 60wt%, and the core material of the microcapsules does not start to lose until heated to about 150°C.
  • a method for preparing double-shell phase change microcapsules includes the following steps:
  • phase change microcapsules were controlled at a stirring speed of 400 rpm, stirred at a constant temperature of 58°C for 120 minutes, filtered, washed with water, and dried to obtain a double-shell phase change microcapsule.
  • the particle size of the double-shell phase change microcapsules is 30-100 ⁇ m.
  • Example 3 The same method as in Example 1 was used to test the solvent resistance of the double-shell phase-change microcapsules, and the double-shell phase-change microcapsules were soaked in water, n-hexane, xylene and ethyl acetate. After 20 days, the core material loss rates were 6.5%, 5.1%, 9.2% and 12.2%.
  • phase change enthalpy of the phase change microcapsules is about 218 J/g.
  • the core material content of the phase-change microcapsules is measured to be about 70wt%, and the core material of the microcapsules starts to lose when heated to about 150°C.
  • a method for preparing double-shell phase change microcapsules includes the following steps:
  • phase change microcapsules were controlled at a stirring speed of 400 rpm, stirred at a constant temperature of 58°C for 120 minutes, filtered, washed with water, and dried to obtain a double-shell phase change microcapsule.
  • the particle size of the double-shell phase change microcapsules is 10-80 ⁇ m.
  • Example 3 The same method as in Example 1 was used to test the solvent resistance of the double-shell phase-change microcapsules, and the double-shell phase-change microcapsules were soaked in water, n-hexane, xylene and ethyl acetate. After 20 days, the core material loss rate was 5.5%, 3.0%, 8.0% and 11.0%, respectively.
  • phase change enthalpy of the phase change microcapsules is about 203 J/g.
  • the core material content of the phase-change microcapsules is measured to be about 70wt%, and the core material of the microcapsules starts to lose when heated to about 150°C.

Abstract

Disclosed is a double-shell phase change microcapsule composed of a core material, an inner shell and an outer shell, wherein the core material is a phase change material, the inner shell is composed of polyurea or/and polyurethane, and the outer shell is composed of polyurea-formaldehyde.

Description

一种双层壳体相变微胶囊及其制备方法 Double-shell phase change microcapsule and preparation method thereof To
技术领域Technical field
本发明涉及一种双层壳体相变微胶囊及其制备方法，属于微胶囊相变材料技术领域。The invention relates to a double-shell phase change microcapsule and a preparation method thereof, and belongs to the technical field of microcapsule phase change materials.
背景技术Background technique
相变材料（Phase Change Material，简称PCM）是指在发生相变时可以吸收或释放大量能量（即相变焓）的一类材料。相变材料种类很多，可以依照不同的分类方法进行分类，例如：按照相变方式可以分为固-固相变材料、固-液相变材料和固-气相变材料；按照材料种类可以分为无机相变材料、有机相变材料和复合相变材料。Phase change material Material, PCM for short) refers to a type of material that can absorb or release a large amount of energy (that is, the enthalpy of phase change) when a phase change occurs. There are many types of phase change materials, which can be classified according to different classification methods. For example, they can be divided into solid-solid phase change materials, solid-liquid phase change materials, and solid-gas phase change materials according to the phase change method; Inorganic phase change materials, organic phase change materials and composite phase change materials.
相变材料发生相变时，需要从环境中吸热或向环境放热，且其物理状态也会发生改变。相变材料物理状态发生变化时可储存或释放的能量称为相变热。相变材料可以通过相转变实现热量存储，是一种重要的潜热存储材料，具有很好的潜在应用前景。When a phase change material undergoes a phase change, it needs to absorb heat from the environment or release heat to the environment, and its physical state will also change. The energy that can be stored or released when the physical state of a phase change material changes is called phase change heat. Phase change materials can realize heat storage through phase transition and are an important latent heat storage material with good potential application prospects.
然而，固-液相变材料发生相变时，存在易泄漏、腐蚀性、体积不稳定、易发生相分离、传热性能差等缺陷。为了解决上述问题，人们将相变材料胶囊化，当胶囊粒径为微米或纳米级时，不仅可以增加胶囊的比表面积以及传热面积，而且还可以提高胶囊的储/放热速率，从而扩展了相变材料的应用范围，例如：将相变材料直接应用于建筑，会出现相变材料外渗和建筑墙体表面结霜等问题，而将相变材料制备成微/纳米胶囊再用于建筑材料时便不会出现这些问题。However, when the solid-liquid phase change material undergoes phase change, it has defects such as easy leakage, corrosiveness, unstable volume, easy phase separation, and poor heat transfer performance. In order to solve the above problems, people encapsulate the phase change material. When the particle size of the capsule is micron or nanometer, it can not only increase the specific surface area and heat transfer area of the capsule, but also increase the heat storage/release rate of the capsule, thereby expanding The application range of phase change materials, for example, if the phase change materials are directly applied to buildings, there will be problems such as the extravasation of the phase change materials and the frosting on the surface of the building walls, and the phase change materials are prepared into micro/nano capsules and then used These problems do not arise when building materials.
目前，常见的相变微胶囊一般是以三聚氰胺、聚脲、聚氨酯、聚脲醛等为壳体，且多是采用单一种类的壳材进行包裹，壳体存在过硬或过软等问题，导致壳体伸缩性差、耐高温性差、冷热循环性能较差和耐溶剂差。此外，单层壳体对水及有机溶剂的耐受性较差，易发生破裂。所以，相变微胶囊的实际应用受到了很大的限制。At present, common phase change microcapsules generally use melamine, polyurea, polyurethane, polyurea-formaldehyde, etc. as the shell, and most of them are wrapped by a single type of shell material. The shell has problems such as too hard or too soft, which leads to the shell Poor flexibility, poor high temperature resistance, poor thermal cycle performance and poor solvent resistance. In addition, the single-layer shell has poor resistance to water and organic solvents and is prone to cracking. Therefore, the practical application of phase change microcapsules is greatly restricted.
发明内容Summary of the invention
本发明的目的在于提供一种双层壳体相变微胶囊及其制备方法。The purpose of the present invention is to provide a double-shell phase change microcapsule and a preparation method thereof.
本发明所采取的技术方案是：The technical scheme adopted by the present invention is:
一种双层壳体相变微胶囊，由芯材、内层壳体和外层壳体组成，所述芯材为相变材料，所述内层壳体由聚脲或/和聚氨酯组成，所述外层壳体由聚脲醛组成。A two-layer shell phase change microcapsule is composed of a core material, an inner shell and an outer shell, the core material is a phase change material, and the inner shell is composed of polyurea or/and polyurethane, The outer shell is composed of polyurea-formaldehyde.
优选的，所述相变材料为C14～C34的直链烷烃、C12～C34的长链脂肪酸中的至少一种。Preferably, the phase change material is at least one of C 14 to C 34 linear alkanes and C 12 to C 34 long chain fatty acids.
进一步优选的，所述相变材料为石蜡、月桂酸、十八酸中的至少一种。Further preferably, the phase change material is at least one of paraffin, lauric acid, and octadecanoic acid.
优选的，相变微胶囊的粒径为0.5～500μm，芯材占比为20wt%～80wt%。Preferably, the particle size of the phase change microcapsules is 0.5-500 μm, and the core material accounts for 20-80 wt%.
上述双层壳体相变微胶囊的制备方法，包括以下步骤：The preparation method of the above-mentioned double-shell phase change microcapsule includes the following steps:
1) 将乳化剂均匀分散在水中配制成乳化剂溶液，再将相变材料和异氰酸酯混合均匀后加入乳化剂溶液中，30～70℃恒温搅拌5～60min，得到水包油乳液；1) Disperse the emulsifier uniformly in water to prepare an emulsifier solution, then mix the phase change material and isocyanate evenly, add to the emulsifier solution, stir at a constant temperature of 30-70°C for 5-60 minutes to obtain an oil-in-water emulsion;
2) 将多元醇或/和多元胺加水分散均匀后加入水包油乳液中，30～70℃恒温搅拌10～150min，再过滤、洗涤，得到单层壳体相变微胶囊；2) Disperse the polyol or/and polyamine with water evenly, add it to the oil-in-water emulsion, stir at a constant temperature of 30 to 70°C for 10 to 150 minutes, filter and wash, to obtain a single-layer shell phase change microcapsule;
3) 将尿素加入甲醛溶液中，调节pH值至7.5～9.0，50～80℃恒温搅拌30～90min，得到尿素-甲醛低聚物；3) Add urea to the formaldehyde solution, adjust the pH to 7.5-9.0, and stir at 50-80°C for 30-90 minutes at a constant temperature to obtain urea-formaldehyde oligomer;
4) 将分散剂和多元酚加水分散均匀后加入尿素-甲醛低聚物中，调节pH值至2.5～3.5，再加入单层壳体相变微胶囊，45～70℃恒温搅拌30～300min，再过滤、洗涤、干燥，得到双层壳体相变微胶囊。4) Disperse the dispersant and polyphenol evenly with water and add them to the urea-formaldehyde oligomer, adjust the pH to 2.5-3.5, then add the single-layer shell phase change microcapsules, stir at 45-70°C for 30-300 minutes, and filter , Washing and drying to obtain phase change microcapsules with double shells.
优选的，上述双层壳体相变微胶囊的制备方法，包括以下步骤：Preferably, the method for preparing the above-mentioned double-shell phase change microcapsules includes the following steps:
1) 将乳化剂均匀分散在水中配制成乳化剂溶液，再将相变材料和异氰酸酯混合均匀后加入乳化剂溶液中，控制搅拌速度为200～2000rpm，30～70℃恒温搅拌5～60min，得到水包油乳液；1) Disperse the emulsifier uniformly in water to prepare an emulsifier solution, then mix the phase change material and isocyanate uniformly and add to the emulsifier solution, control the stirring speed to 200-2000rpm, stir at 30-70°C for 5-60min, and obtain the water bag Oil emulsion
2) 将多元醇或/和多元胺加水分散均匀后加入水包油乳液中，控制搅拌速度为200～1200rpm，30～70℃恒温搅拌10～150min，再过滤、洗涤，得到单层壳体相变微胶囊；2) Disperse the polyol or/and polyamine with water evenly and add it to the oil-in-water emulsion, control the stirring speed to 200-1200rpm, stir at a constant temperature of 30-70°C for 10-150min, filter and wash again, to obtain a single-layer shell with phase change capsule;
3) 将尿素加入甲醛溶液中，调节pH值至7.5～9.0，控制搅拌速度为100～600rpm，50～80℃恒温搅拌30～90min，得到尿素-甲醛低聚物；3) Add urea to the formaldehyde solution, adjust the pH to 7.5-9.0, control the stirring speed at 100-600 rpm, and stir at 50-80°C for 30-90 minutes to obtain urea-formaldehyde oligomer;
4) 将分散剂和多元酚加水分散均匀后加入尿素-甲醛低聚物中，调节pH值至2.5～3.5，再加入单层壳体相变微胶囊，控制搅拌速度为100～600rpm，45～70℃恒温搅拌30～300min，再过滤、洗涤、干燥，得到双层壳体相变微胶囊。4) Disperse the dispersant and polyphenol evenly with water and add them to the urea-formaldehyde oligomer, adjust the pH to 2.5-3.5, then add the monolayer shell phase change microcapsules, control the stirring speed at 100-600rpm, 45-70℃ Stir at a constant temperature for 30-300 minutes, then filter, wash, and dry to obtain phase change microcapsules with double shells.
优选的，所述相变材料、异氰酸酯、多元醇或/和多元胺、尿素、甲醛、多元酚的质量比为1：（0.025～0.250）：（0.05～0.25）：（0.05～0.50）：（0.05～1.00）：（0.025～0.500）。Preferably, the mass ratio of the phase change material, isocyanate, polyol or/and polyamine, urea, formaldehyde, and polyphenol is 1:(0.025～0.250):(0.05～0.25):(0.05～0.50):( 0.05～1.00): (0.025～0.500).
优选的，步骤1）所述相变材料、乳化剂的质量比为1：（0.015～0.150）。Preferably, the mass ratio of the phase change material and emulsifier in step 1) is 1: (0.015 to 0.150).
优选的，步骤1）所述乳化剂为***胶、聚乙烯醇、乳化剂OP-10中的至少一种。Preferably, the emulsifier in step 1) is at least one of gum arabic, polyvinyl alcohol, and emulsifier OP-10.
优选的，步骤1）所述异氰酸酯为HDI、MDI、IPDI、HDI二聚体、HDI三聚体中的至少一种。Preferably, the isocyanate in step 1) is at least one of HDI, MDI, IPDI, HDI dimer, and HDI trimer.
优选的，步骤2）所述多元醇为1,4-二丁醇、1,6-己二醇、丙三醇、山梨醇、聚醚多元醇中的至少一种。Preferably, the polyol in step 2) is at least one of 1,4-dibutanol, 1,6-hexanediol, glycerol, sorbitol, and polyether polyol.
优选的，步骤2）所述多元胺为1,6-己二胺、三乙烯四胺、四乙烯五胺、聚乙烯亚胺中的至少一种。Preferably, in step 2), the polyamine is at least one of 1,6-hexanediamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine.
优选的，步骤3）所述甲醛溶液的质量分数为37%～40%。Preferably, the mass fraction of the formaldehyde solution in step 3) is 37%-40%.
优选的，所述相变材料、分散剂的质量比为1：（0.025～0.500）。Preferably, the mass ratio of the phase change material to the dispersant is 1: (0.025 to 0.500).
优选的，步骤4）所述分散剂为乙烯-马来酸酐共聚物、苯乙烯-马来酸酐共聚物、***胶中的至少一种。Preferably, the dispersant in step 4) is at least one of ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and gum arabic.
优选的，步骤4）所述多元酚为邻苯二酚、间苯二酚、对苯二酚中的至少一种。Preferably, the polyhydric phenol in step 4) is at least one of catechol, resorcinol, and hydroquinone.
本发明的有益效果是：本发明的相变微胶囊具有良好的耐高温性能、耐冷热循环性能和耐溶剂性能，且制备工艺简单、生产成本低，可以广泛应用于建筑、纺织服装、电子产品、军事等领域。The beneficial effects of the present invention are: the phase change microcapsules of the present invention have good high temperature resistance, cold and heat cycle resistance and solvent resistance, simple preparation process, low production cost, and can be widely used in construction, textile and clothing, electronics Products, military and other fields.
1）本发明的相变微胶囊升温至150℃以上时芯材才会出现挥发，进行100次-5℃至60℃冷热循环后相变微胶囊的熔化-凝固曲线的峰形不变，熔化焓基本维持不变，耐高温性能和耐冷热循环性能优良；1) The core material of the phase change microcapsules of the present invention will not volatilize until the temperature rises above 150°C, and the peak shape of the melting-solidification curve of the phase change microcapsules remains unchanged after 100 cycles of -5°C to 60°C. The enthalpy of fusion remains basically unchanged, and the high temperature resistance and thermal cycle resistance are excellent;
2）本发明的相变微胶囊在水、正己烷、二甲苯、乙酸乙酯等溶剂中连续浸泡20天后芯材损失率仅6%～11%，耐溶剂性能优良。2) The phase change microcapsule of the present invention has a core material loss rate of only 6%-11% after continuous immersion in water, n-hexane, xylene, ethyl acetate and other solvents for 20 days, and has excellent solvent resistance.
附图说明Description of the drawings
图1为实施例1的双层壳体相变微胶囊的SEM图。FIG. 1 is an SEM image of the double-shell phase change microcapsule of Example 1. FIG.
图2为实施例1的双层壳体相变微胶囊进行1次和100次冷热循环后的熔化-凝固曲线。Fig. 2 shows the melting-solidification curves of the double-shell phase change microcapsules of Example 1 after one and 100 heat and cold cycles.
图3为实施例1的双层壳体相变微胶囊的DSC图。3 is a DSC chart of the double-shell phase change microcapsules of Example 1. FIG.
图4为实施例1的双层壳体相变微胶囊的TGA图。4 is a TGA diagram of the double-shell phase change microcapsule of Example 1. FIG.
图5为实施例2的双层壳体相变微胶囊的SEM图。FIG. 5 is an SEM image of the double-shell phase change microcapsule of Example 2. FIG.
图6为实施例2的双层壳体相变微胶囊的DSC图。6 is a DSC chart of the double-shell phase change microcapsules of Example 2.
图7为实施例2的双层壳体相变微胶囊的TGA图。7 is a TGA diagram of the double-shell phase change microcapsule of Example 2.
图8为实施例3的双层壳体相变微胶囊的SEM图。FIG. 8 is an SEM image of the double-shell phase change microcapsule of Example 3. FIG.
图9为实施例3的双层壳体相变微胶囊的DSC图。9 is a DSC chart of the double-shell phase change microcapsule of Example 3.
图10为实施例4的双层壳体相变微胶囊的SEM图。FIG. 10 is an SEM image of the double-shell phase change microcapsule of Example 4. FIG.
图11为实施例4的双层壳体相变微胶囊的DSC图。11 is a DSC chart of the double-shell phase change microcapsules of Example 4. FIG.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的解释和说明。The present invention will be further explained and illustrated below in conjunction with specific embodiments.
实施例1：Example 1:
一种双层壳体相变微胶囊的制备方法，包括以下步骤：A method for preparing double-shell phase change microcapsules includes the following steps:
1）将3g的***胶均匀分散在100g的水中配制成乳化剂溶液，再将25g的石蜡PCM35（相变温度35℃）和3g的HDI混合均匀后加入乳化剂溶液中，控制搅拌速度为1200rpm，40℃恒温搅拌20min，得到水包油乳液；1) Disperse 3g of gum arabic evenly in 100g of water to prepare an emulsifier solution, then mix 25g of paraffin wax PCM35 (phase transition temperature 35℃) and 3g of HDI and add it to the emulsifier solution, control the stirring speed to 1200rpm , Stir at a constant temperature of 40°C for 20 minutes to obtain an oil-in-water emulsion;
2）将6g的四乙烯五胺加水分散均匀后加入水包油乳液中，控制搅拌速度为600rpm，60℃恒温搅拌50min，再过滤、水洗，得到单层壳体相变微胶囊；2) Disperse 6g of tetraethylenepentamine with water and add it to the oil-in-water emulsion, control the stirring speed to 600rpm, stir at a constant temperature of 60°C for 50min, filter and wash with water to obtain a single-layer shell phase change microcapsule;
3）将8g的尿素加入20g质量分数37%的甲醛溶液中，调节pH值至8.5，控制搅拌速度为400rpm，65℃恒温搅拌50min，得到尿素-甲醛低聚物；3) Add 8g of urea to 20g of 37% formaldehyde solution, adjust the pH to 8.5, control the stirring speed to 400rpm, and stir at 65°C for 50min to obtain urea-formaldehyde oligomer;
4）将3g的聚乙烯-马来酸酐共聚物和3g的间苯二酚加150g的水分散均匀后加入尿素-甲醛低聚物中，调节pH值至3.3，再加入单层壳体相变微胶囊，控制搅拌速度为400rpm，52℃恒温搅拌100min，再过滤、水洗、干燥，得到双层壳体相变微胶囊。4) Disperse 3g of polyethylene-maleic anhydride copolymer and 3g of resorcinol with 150g of water, then add it to the urea-formaldehyde oligomer, adjust the pH to 3.3, and then add the single-layer shell for phase change For microcapsules, the stirring speed is controlled to 400rpm, and the temperature is kept at 52°C for 100min, followed by filtering, washing and drying to obtain phase change microcapsules with double shells.
性能测试：Performance Testing:
1）双层壳体相变微胶囊的扫描电镜图（SEM）如图1所示。1) The scanning electron microscope image (SEM) of the double-shell phase-change microcapsule is shown in Figure 1.
由图1可知：相变微胶囊的粒径为20～60μm。It can be seen from Figure 1 that the particle size of the phase change microcapsules is 20-60 μm.
2）双层壳体相变微胶囊进行1次和100次-5℃至60℃的冷热循环后的熔化-凝固曲线如图2所示。2) Figure 2 shows the melting-solidification curve of the double-shell phase change microcapsules after one time and 100 cycles of -5°C to 60°C.
由图2可知：双层壳体相变微胶囊进行100次-5℃至60℃的冷热循环后，熔化-凝固曲线的峰形保持不变，且熔化焓仅改变了0.36%。It can be seen from Fig. 2 that the peak shape of the melting-solidification curve remains unchanged after the double-shell phase-change microcapsule undergoes 100 thermal cycles of -5°C to 60°C, and the melting enthalpy only changes by 0.36%.
3）将双层壳体相变微胶囊分别浸泡在水、正己烷、二甲苯和乙酸乙酯中，20天后测试芯材损失率，测试得到芯材损失率分别为6.0%、4.0%、8.4%和10.8%。3) The double-shell phase change microcapsules were immersed in water, n-hexane, xylene and ethyl acetate respectively. After 20 days, the core material loss rate was tested, and the core material loss rate was 6.0%, 4.0%, and 8.4. % And 10.8%.
4）双层壳体相变微胶囊的DSC图如图3所示。4) The DSC chart of the double shell phase change microcapsule is shown in Figure 3.
由图3可知：相变微胶囊的相变焓约200J/g。It can be seen from Figure 3 that the phase change enthalpy of the phase change microcapsules is about 200J/g.
5）双层壳体相变微胶囊的TGA图如图4所示。5) The TGA diagram of the double shell phase change microcapsule is shown in Figure 4.
由图4可知：相变微胶囊的芯材含量约73wt%，微胶囊芯材在加热到150℃左右才开始损失。It can be seen from Figure 4 that the core material content of the phase change microcapsules is about 73wt%, and the core material of the microcapsules does not start to lose until heated to about 150°C.
实施例2：Example 2:
一种双层壳体相变微胶囊的制备方法，包括以下步骤：A method for preparing double-shell phase change microcapsules includes the following steps:
1）将2g的PVA-1788均匀分散在70g的水中配制成乳化剂溶液，再将20g的石蜡PCM48（相变温度48℃）和2g的MDI混合均匀后加入乳化剂溶液中，控制搅拌速度为1000rpm，55℃恒温搅拌15min，得到水包油乳液；1) Disperse 2g of PVA-1788 uniformly in 70g of water to prepare an emulsifier solution, then mix 20g of paraffin wax PCM48 (phase transition temperature 48℃) and 2g of MDI and add it to the emulsifier solution. Control the stirring speed to Stir at 1000 rpm and 55°C for 15 minutes to obtain an oil-in-water emulsion;
2）将5g的PEI1800加水分散均匀后加入水包油乳液中，控制搅拌速度为300rpm，65℃恒温搅拌70min，再过滤、水洗，得到单层壳体相变微胶囊；2) Disperse 5g of PEI1800 with water evenly and add it to the oil-in-water emulsion, control the stirring speed to 300rpm, stir at 65°C for 70min, filter and wash with water to obtain the single-layer shell phase change microcapsules;
3）将5g的尿素加入13g质量分数37%的甲醛溶液中，调节pH值至8.2，控制搅拌速度为500rpm，75℃恒温搅拌45min，得到尿素-甲醛低聚物；3) Add 5g of urea to 13g of 37% formaldehyde solution, adjust the pH to 8.2, control the stirring speed to 500rpm, and stir at 75°C for 45min to obtain urea-formaldehyde oligomer;
4）将2.5g的聚乙烯-马来酸酐共聚物和3.5g的间苯二酚加120g的水分散均匀后加入尿素-甲醛低聚物中，调节pH值至2.9，再加入单层壳体相变微胶囊，控制搅拌速度为400rpm，58℃恒温搅拌120min，再过滤、水洗、干燥，得到双层壳体相变微胶囊。4) Disperse 2.5g of polyethylene-maleic anhydride copolymer and 3.5g of resorcinol with 120g of water evenly, then add it to the urea-formaldehyde oligomer, adjust the pH to 2.9, and then add the single-layer shell The phase change microcapsules were controlled at a stirring speed of 400 rpm, stirred at a constant temperature of 58°C for 120 minutes, filtered, washed with water, and dried to obtain a double-shell phase change microcapsule.
性能测试：Performance Testing:
1）双层壳体相变微胶囊的扫描电镜图（SEM）如图5所示。1) The scanning electron microscope image (SEM) of the double-shell phase-change microcapsule is shown in Figure 5.
由图5可知：相变微胶囊的粒径为40～90μm。It can be seen from Figure 5 that the particle size of the phase change microcapsules is 40 to 90 μm.
2）采用和实施例1相同的方法对双层壳体相变微胶囊进行冷热循环测试，测试得到双层壳体相变微胶囊进行100次-5℃至60℃的冷热循环后，熔化-凝固曲线的峰形保持不变，且熔化焓仅改变了3.0%。2) The double-shell phase change microcapsules were subjected to the cold and heat cycle test using the same method as in Example 1. After the double-shell phase change microcapsules were subjected to 100 heat and cold cycles at -5°C to 60°C, The peak shape of the melting-solidification curve remains unchanged, and the melting enthalpy only changes by 3.0%.
3）采用和实施例1相同的方法对双层壳体相变微胶囊进行耐溶剂性能测试，测试得到双层壳体相变微胶囊分别在水、正己烷、二甲苯和乙酸乙酯中浸泡20天后，芯材损失率分别为5.0%、3.5%、7.0%和9.6%。3) The same method as in Example 1 was used to test the solvent resistance of the double-shell phase-change microcapsules, and the double-shell phase-change microcapsules were soaked in water, n-hexane, xylene and ethyl acetate. After 20 days, the core material loss rate was 5.0%, 3.5%, 7.0% and 9.6% respectively.
4）双层壳体相变微胶囊的DSC图如图6所示。4) The DSC chart of the double-shell phase change microcapsule is shown in Figure 6.
由图6可知：相变微胶囊的相变焓约130J/g。It can be seen from Figure 6 that the phase change enthalpy of the phase change microcapsules is about 130 J/g.
5）双层壳体相变微胶囊的TGA图如图7所示。5) The TGA diagram of the double-shell phase change microcapsule is shown in Figure 7.
由图7可知：相变微胶囊的芯材含量约60wt%，微胶囊芯材在加热到150℃左右才开始损失。It can be seen from Fig. 7 that the core material content of the phase change microcapsules is about 60wt%, and the core material of the microcapsules does not start to lose until heated to about 150°C.
实施例3：Example 3:
一种双层壳体相变微胶囊的制备方法，包括以下步骤：A method for preparing double-shell phase change microcapsules includes the following steps:
1）将2.5g的PVA-1788均匀分散在80g的水中配制成乳化剂溶液，再将20g的石蜡PCM48（相变温度48℃）和3g的MDI混合均匀后加入乳化剂溶液中，控制搅拌速度为1100rpm，55℃恒温搅拌15min，得到水包油乳液；1) Disperse 2.5g of PVA-1788 evenly in 80g of water to prepare an emulsifier solution, then mix 20g of paraffin wax PCM48 (phase transition temperature 48℃) and 3g of MDI and add it to the emulsifier solution, control the stirring speed Stir at a constant temperature of 1100 rpm at 55°C for 15 minutes to obtain an oil-in-water emulsion;
2）将3g的PEI1800加水分散均匀后加入水包油乳液中，控制搅拌速度为350rpm，65℃恒温搅拌70min，再过滤、水洗，得到单层壳体相变微胶囊；2) Disperse 3g of PEI1800 evenly in water and add it to the oil-in-water emulsion, control the stirring speed to 350rpm, stir at 65°C for 70min, filter and wash with water to obtain monolayer shell phase change microcapsules;
3）将7.5g的尿素加入19g质量分数37%的甲醛溶液中，调节pH值至8.2，控制搅拌速度为500rpm，75℃恒温搅拌45min，得到尿素-甲醛低聚物；3) Add 7.5g of urea to 19g of 37% formaldehyde solution, adjust the pH to 8.2, control the stirring speed to 500rpm, and stir for 45min at 75°C to obtain urea-formaldehyde oligomer;
4）将1.5g的聚乙烯-马来酸酐共聚物和4.5g的间苯二酚加120g的水分散均匀后加入尿素-甲醛低聚物中，调节pH值至3.1，再加入单层壳体相变微胶囊，控制搅拌速度为400rpm，58℃恒温搅拌120min，再过滤、水洗、干燥，得到双层壳体相变微胶囊。4) Disperse 1.5g of polyethylene-maleic anhydride copolymer and 4.5g of resorcinol with 120g of water and add it to the urea-formaldehyde oligomer, adjust the pH to 3.1, and then add the single-layer shell The phase change microcapsules were controlled at a stirring speed of 400 rpm, stirred at a constant temperature of 58°C for 120 minutes, filtered, washed with water, and dried to obtain a double-shell phase change microcapsule.
性能测试：Performance Testing:
1）双层壳体相变微胶囊的扫描电镜图（SEM）如图8所示。1) The scanning electron microscope image (SEM) of the double-shell phase change microcapsule is shown in Figure 8.
由图8可知：双层壳体相变微胶囊的粒径为30～100μm。It can be seen from Figure 8 that the particle size of the double-shell phase change microcapsules is 30-100 μm.
2）采用和实施例1相同的方法对双层壳体相变微胶囊进行冷热循环测试，测试得到双层壳体相变微胶囊进行100次-5℃至60℃的冷热循环后，熔化-凝固曲线的峰形保持不变，且熔化焓仅改变了0.39%。2) The double-shell phase change microcapsules were subjected to the cold and heat cycle test using the same method as in Example 1. After the double-shell phase change microcapsules were subjected to 100 heat and cold cycles at -5°C to 60°C, The peak shape of the melting-solidification curve remains unchanged, and the enthalpy of melting only changes by 0.39%.
3）采用和实施例1相同的方法对双层壳体相变微胶囊进行耐溶剂性能测试，测试得到双层壳体相变微胶囊分别在水、正己烷、二甲苯和乙酸乙酯中浸泡20天后，芯材损失率分别为6.5%、5.1%、9.2%和12.2%。3) The same method as in Example 1 was used to test the solvent resistance of the double-shell phase-change microcapsules, and the double-shell phase-change microcapsules were soaked in water, n-hexane, xylene and ethyl acetate. After 20 days, the core material loss rates were 6.5%, 5.1%, 9.2% and 12.2%.
4）双层壳体相变微胶囊的DSC图如图9所示。4) The DSC chart of the double shell phase change microcapsule is shown in Figure 9.
由图9可知：相变微胶囊的相变焓约218J/g。It can be seen from Fig. 9 that the phase change enthalpy of the phase change microcapsules is about 218 J/g.
5）通过TGA测试，测得相变微胶囊的芯材含量约70wt%，微胶囊芯材在加热到150℃左右才开始损失。5) Through the TGA test, the core material content of the phase-change microcapsules is measured to be about 70wt%, and the core material of the microcapsules starts to lose when heated to about 150°C.
实施例4：Example 4:
一种双层壳体相变微胶囊的制备方法，包括以下步骤：A method for preparing double-shell phase change microcapsules includes the following steps:
1）将1.5g的PVA-1788均匀分散在70g的水中配制成乳化剂溶液，再将20g的石蜡PCM48（相变温度48℃）和1.5g的MDI混合均匀后加入乳化剂溶液中，控制搅拌速度为1000rpm，55℃恒温搅拌15min，得到水包油乳液；1) Disperse 1.5g of PVA-1788 evenly in 70g of water to prepare an emulsifier solution, then mix 20g of paraffin wax PCM48 (phase transition temperature 48℃) and 1.5g of MDI and add it to the emulsifier solution, control the stirring Stir at a speed of 1000 rpm at a constant temperature of 55°C for 15 minutes to obtain an oil-in-water emulsion;
2）将2g的PEI1800加水分散均匀后加入水包油乳液中，控制搅拌速度为300rpm，65℃恒温搅拌70min，再过滤、水洗，得到单层壳体相变微胶囊；2) Disperse 2g of PEI1800 with water evenly and then add it to the oil-in-water emulsion, control the stirring speed to 300rpm, stir at 65°C for 70min, filter and wash with water to obtain single-layer shell phase change microcapsules;
3）将5g的尿素加入13g质量分数37%的甲醛溶液中，调节pH值至8.2，控制搅拌速度为500rpm，75℃恒温搅拌45min，得到尿素-甲醛低聚物；3) Add 5g of urea to 13g of 37% formaldehyde solution, adjust the pH to 8.2, control the stirring speed to 500rpm, and stir at 75°C for 45min to obtain urea-formaldehyde oligomer;
4）将1.2g的聚乙烯-马来酸酐共聚物和4.0g的间苯二酚加120g的水分散均匀后加入尿素-甲醛低聚物中，调节pH值至3.0，再加入单层壳体相变微胶囊，控制搅拌速度为400rpm，58℃恒温搅拌120min，再过滤、水洗、干燥，得到双层壳体相变微胶囊。4) Disperse 1.2g of polyethylene-maleic anhydride copolymer and 4.0g of resorcinol with 120g of water and add it to the urea-formaldehyde oligomer, adjust the pH to 3.0, and then add the single-layer shell The phase change microcapsules were controlled at a stirring speed of 400 rpm, stirred at a constant temperature of 58°C for 120 minutes, filtered, washed with water, and dried to obtain a double-shell phase change microcapsule.
性能测试：Performance Testing:
1）双层壳体相变微胶囊的扫描电镜图（SEM）如图10所示。1) The scanning electron microscope image (SEM) of the double-shell phase-change microcapsule is shown in Figure 10.
由图10可知：双层壳体相变微胶囊的粒径为10～80μm。It can be seen from Figure 10 that the particle size of the double-shell phase change microcapsules is 10-80 μm.
2）采用和实施例1相同的方法对双层壳体相变微胶囊进行冷热循环测试，测试得到双层壳体相变微胶囊进行100次-5℃至60℃的冷热循环后，熔化-凝固曲线的峰形保持不变，且熔化焓仅改变了2.8%。2) The double-shell phase change microcapsules were subjected to the cold and heat cycle test using the same method as in Example 1. After the double-shell phase change microcapsules were subjected to 100 heat and cold cycles at -5°C to 60°C, The peak shape of the melting-solidification curve remains unchanged, and the melting enthalpy only changes by 2.8%.
3）采用和实施例1相同的方法对双层壳体相变微胶囊进行耐溶剂性能测试，测试得到双层壳体相变微胶囊分别在水、正己烷、二甲苯和乙酸乙酯中浸泡20天后，芯材损失率分别为5.5%、3.0%、8.0%和11.0%。3) The same method as in Example 1 was used to test the solvent resistance of the double-shell phase-change microcapsules, and the double-shell phase-change microcapsules were soaked in water, n-hexane, xylene and ethyl acetate. After 20 days, the core material loss rate was 5.5%, 3.0%, 8.0% and 11.0%, respectively.
4）双层壳体相变微胶囊的DSC图如图11所示。4) The DSC chart of the double shell phase change microcapsules is shown in Figure 11.
由图11可知：相变微胶囊的相变焓约203J/g。It can be seen from Fig. 11 that the phase change enthalpy of the phase change microcapsules is about 203 J/g.
5）通过TGA测试，测得相变微胶囊的芯材含量约70wt%，微胶囊芯材在加热到150℃左右才开始损失。5) Through the TGA test, the core material content of the phase-change microcapsules is measured to be about 70wt%, and the core material of the microcapsules starts to lose when heated to about 150°C.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, etc. made without departing from the spirit and principle of the present invention Simplified, all should be equivalent replacement methods, and they are all included in the protection scope of the present invention.

Claims (10)

  1. 一种双层壳体相变微胶囊，其特征在于：由芯材、内层壳体和外层壳体组成，所述芯材为相变材料，所述内层壳体由聚脲或/和聚氨酯组成，所述外层壳体由聚脲醛组成。 A two-layer shell phase change microcapsule, which is characterized in that it is composed of a core material, an inner shell and an outer shell, the core material is a phase change material, and the inner shell is made of polyurea or/ And polyurethane, and the outer shell is made of polyurea-formaldehyde. To
  2. 根据权利要求1所述的双层壳体相变微胶囊，其特征在于：所述相变材料为C14～C34的直链烷烃、C12～C34的长链脂肪酸中的至少一种。The double-shell phase change microcapsule according to claim 1, wherein the phase change material is at least one of C 14 to C 34 linear alkanes and C 12 to C 34 long chain fatty acids .
  3. 根据权利要求2所述的双层壳体相变微胶囊，其特征在于：所述相变材料为石蜡、月桂酸、十八酸中的至少一种。The double-shell phase change microcapsule according to claim 2, wherein the phase change material is at least one of paraffin, lauric acid, and octadecanoic acid.
  4. 根据权利要求1或2所述的双层壳体相变微胶囊，其特征在于：相变微胶囊的粒径为0.5～500μm，芯材占比为20wt%～80wt%。The double-shell phase change microcapsule according to claim 1 or 2, characterized in that the particle size of the phase change microcapsule is 0.5-500 μm, and the core material accounts for 20 wt% to 80 wt%.
  5. 权利要求1～4中任意一项所述的双层壳体相变微胶囊的制备方法，其特征在于：包括以下步骤：The method for preparing double-shell phase change microcapsules according to any one of claims 1 to 4, characterized in that it comprises the following steps:
    1) 将乳化剂均匀分散在水中配制成乳化剂溶液，再将相变材料和异氰酸酯混合均匀后加入乳化剂溶液中，30～70℃恒温搅拌5～60min，得到水包油乳液；1) Disperse the emulsifier uniformly in water to prepare an emulsifier solution, then mix the phase change material and isocyanate evenly, add to the emulsifier solution, stir at a constant temperature of 30-70°C for 5-60 minutes to obtain an oil-in-water emulsion;
    2) 将多元醇或/和多元胺加水分散均匀后加入水包油乳液中，30～70℃恒温搅拌10～150min，再过滤、洗涤，得到单层壳体相变微胶囊；2) Disperse the polyol or/and polyamine with water evenly, add it to the oil-in-water emulsion, stir at a constant temperature of 30 to 70°C for 10 to 150 minutes, filter and wash, to obtain a single-layer shell phase change microcapsule;
    3) 将尿素加入甲醛溶液中，调节pH值至7.5～9.0，50～80℃恒温搅拌30～90min，得到尿素-甲醛低聚物；3) Add urea to the formaldehyde solution, adjust the pH to 7.5-9.0, and stir at 50-80°C for 30-90 minutes at a constant temperature to obtain urea-formaldehyde oligomer;
    4) 将分散剂和多元酚加水分散均匀后加入尿素-甲醛低聚物中，调节pH值至2.5～3.5，再加入单层壳体相变微胶囊，45～70℃恒温搅拌30～300min，再过滤、洗涤、干燥，得到双层壳体相变微胶囊。4) Disperse the dispersant and polyphenol evenly with water and add them to the urea-formaldehyde oligomer, adjust the pH to 2.5-3.5, then add the single-layer shell phase change microcapsules, stir at 45-70°C for 30-300 minutes, and filter , Washing and drying to obtain phase change microcapsules with double shells.
  6. 根据权利要求5所述的制备方法，其特征在于：所述相变材料、异氰酸酯、多元醇或/和多元胺、尿素、甲醛、多元酚的质量比为1：（0.025～0.250）：（0.05～0.25）：（0.05～0.50）：（0.05～1.00）：（0.025～0.500）。The preparation method according to claim 5, characterized in that: the mass ratio of the phase change material, isocyanate, polyol or/and polyamine, urea, formaldehyde, and polyphenol is 1:(0.025～0.250):(0.05 ～0.25): (0.05～0.50): (0.05～1.00): (0.025～0.500).
  7. 根据权利要求5或6所述的制备方法，其特征在于：步骤1）所述乳化剂为***胶、聚乙烯醇、乳化剂OP-10中的至少一种；步骤1）所述异氰酸酯为HDI、MDI、IPDI、HDI二聚体、HDI三聚体中的至少一种。The preparation method according to claim 5 or 6, characterized in that: step 1) the emulsifier is at least one of gum arabic, polyvinyl alcohol, and emulsifier OP-10; step 1) the isocyanate is HDI , At least one of MDI, IPDI, HDI dimer, HDI trimer.
  8. 根据权利要求5或6所述的制备方法，其特征在于：步骤2）所述多元醇为1,4-二丁醇、1,6-己二醇、丙三醇、山梨醇、聚醚多元醇中的至少一种；步骤2）所述多元胺为1,6-己二胺、三乙烯四胺、四乙烯五胺、聚乙烯亚胺中的至少一种。The preparation method according to claim 5 or 6, characterized in that: step 2) the polyol is 1,4-dibutanol, 1,6-hexanediol, glycerol, sorbitol, polyether polyol At least one of alcohols; step 2) the polyamine is at least one of 1,6-hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine.
  9. 根据权利要求5或6所述的制备方法，其特征在于：步骤3）所述甲醛溶液的质量分数为37%～40%。The preparation method according to claim 5 or 6, wherein the mass fraction of the formaldehyde solution in step 3) is 37%-40%.
  10. 根据权利要求5或6所述的制备方法，其特征在于：步骤4）所述分散剂为乙烯-马来酸酐共聚物、苯乙烯-马来酸酐共聚物、***胶中的至少一种；步骤4）所述多元酚为邻苯二酚、间苯二酚、对苯二酚中的至少一种。The preparation method according to claim 5 or 6, characterized in that: step 4) the dispersant is at least one of ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and gum arabic; step 4) The polyhydric phenol is at least one of catechol, resorcinol, and hydroquinone.
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