WO2021109891A1 - 一种聚氨酯改性有机硅树脂为壳材的相变储能微胶囊及其制备方法 - Google Patents

一种聚氨酯改性有机硅树脂为壳材的相变储能微胶囊及其制备方法 Download PDF

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WO2021109891A1
WO2021109891A1 PCT/CN2020/130865 CN2020130865W WO2021109891A1 WO 2021109891 A1 WO2021109891 A1 WO 2021109891A1 CN 2020130865 W CN2020130865 W CN 2020130865W WO 2021109891 A1 WO2021109891 A1 WO 2021109891A1
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silicone resin
prepolymer
polyurethane
energy storage
phase change
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French (fr)
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喻学锋
刘海生
李金堆
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深圳先进电子材料国际创新研究院
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    • 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
    • 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
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    • 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

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  • the invention belongs to the technical field of phase change energy storage, and specifically relates to a phase change energy storage microcapsule with a polyurethane modified silicone resin as a shell material and a preparation method thereof.
  • Phase change energy storage technology is the application of microencapsulation technology to coat a layer of stable film on the surface of solid-liquid phase change energy storage material particles to form a composite phase change energy storage material with a "core-shell" structure.
  • Phase-change energy storage materials will have problems of leakage, volume change and easy corrosion during the application process. Therefore, the phase-change energy storage materials need to be microencapsulated and packaged.
  • the shell materials of phase change energy storage microcapsules can generally be divided into organic shell materials and inorganic shell materials. Most of the inorganic shell materials are through the hydrolysis-condensation of inorganic precursors on the surface of the phase change energy storage materials to achieve phase change. It is coated with variable energy storage materials, but the toughness of the inorganic shell material is poor, and it is easy to crack during use, making it difficult to realize industrialization.
  • the organic shell material has excellent toughness, is easy to process, and is easy to realize industrialization.
  • paraffin@calcium carbonate phase change energy storage microcapsules which use paraffin wax as the core material and calcium carbonate as the shell material.
  • the phase change energy storage microcapsules have poor shell toughness, which is easy to break during processing, and calcium carbonate is not acid resistant and is easy to degrade in an acid environment. It is easy to appear during the drying process of the microcapsules. Agglomeration, it is impossible to form a powder with uniform particle size during drying.
  • phase change energy storage microcapsule reported in the patent publication number CN109868116A uses melamine-formaldehyde resin as the shell material. From the SEM image, it can be seen that the microcapsule has a large number of shell breaking phenomena, indicating that the toughness of the shell material is not enough. At the same time, the phase change energy storage microcapsules of the shell material have carcinogen formaldehyde in the production and use process, which is easy to cause environmental pollution, and will cause physical harm to the operators and users.
  • the present invention aims to provide a polyurethane modified silicone resin shell phase change energy storage microcapsule with excellent shell material toughness, controllable particle size and superior processing performance .
  • the phase change energy storage microcapsules are directly synthesized in the water phase during preparation, which can effectively reduce production costs and reduce environmental pollution; the processing technology is simple, and the product will not cause physical harm to the producer and the user.
  • the present invention adopts the interfacial polymerization method, the polyurethane modified silicone grease prepolymer is used as the oil-soluble reactive monomer, and water is used as the water-soluble reactive monomer.
  • the main reaction formula is as follows:
  • One aspect of the present invention provides a preparation method of a phase change energy storage microcapsule with a polyurethane modified silicone resin as a shell material, which comprises the following steps:
  • the core material is a phase change energy storage material
  • the surfactant is an oil-in-water emulsifier
  • the monomers that generate polysiloxane are vinyl silicone oil and hydrogen-containing silicone oil with a hydrogen content of 0.1 to 2.0.
  • the vinyl silicone oil is selected from methyl vinyl silicone oil, styrene-based silicone oil, divinyl silicone oil, tetramethyl divinyl disiloxane or polyvinyl silicone oil, preferably tetramethyl divinyl disiloxane. Vinyl disiloxane.
  • the hydrogen-containing silicone oil with a hydrogen content of 0.1 to 2.0 is selected from polymethylhydrogensiloxane.
  • the polyurethane prepolymer is a polyurethane prepolymer synthesized from a diisocyanate monomer and a polyether diol as raw materials, and the diisocyanate monomer is selected from diphenylmethane diisocyanate (MDI), 2,4 -Toluene diisocyanate (TDI), isophorone diisocyanate (IPDI) and its dimer or polymer, preferably diphenylmethane diisocyanate monomer, 2,4-toluene diisocyanate monomer and its dimer Or multimers.
  • MDI diphenylmethane diisocyanate
  • TDI 2,4 -Toluene diisocyanate
  • IPDI isophorone diisocyanate
  • dimer or polymer preferably diphenylmethane diisocyanate monomer, 2,4-toluene diisocyanate monomer and its dimer Or multimers.
  • the polyurethane prepolymer is added in an amount of 4%-20% of the polysiloxane prepolymer, preferably 5%-10%.
  • the HLB value of the emulsifier is 8-15, more preferably, the emulsifier is styrene maleic anhydride copolymer sodium salt, sodium dodecylbenzene sulfonate, dodecyl sulfonic acid Sodium, sodium lauryl sulfate, OP-10, Tween 80, cocamidopropyl dimethylamine hydantoin, polyoxyethylene (16) sorbitan monotalloleate, polyoxyethylene ( 10) Sorbitan monolaurate, polyoxyethylene (20) sorbitan dioleate, sodium rosinate, sodium C14-18 alkyl sulfate, dialkylsulfosuccinate or their compound Compound, PVA.
  • the emulsifier is styrene maleic anhydride copolymer sodium salt, sodium dodecylbenzene sulfonate, dodecyl sulfonic acid Sodium, sodium lauryl
  • the catalysts in steps (1) and (5) are independently selected from platinum catalysts and organotin catalysts.
  • the organotin catalyst is dibutyltin dilaurate, stannous octoate, di(decyl) Dialkyl sulfide) dibutyl tin, dibutyl tin diacetate, dibutyl tin diacetate, dibutyl tin dichloride, methyl tin trichloride and trimethyl tin chloride, dibutyl tin didecanoate, zinc isooctanoate, neodecyl
  • the bismuth acid, platinum catalyst is a platinum(0)-divinyltetramethyldisiloxane complex (Karstedt catalyst).
  • the amount of the catalyst in step (1) is 0.025-0.1% of the reaction monomer.
  • the amount of catalyst in step (5) is 5-20 times the amount of catalyst in step (1).
  • the core material is selected from normal alkanes or oil-soluble ester phase change materials
  • the oil-soluble ester phase change material is selected from one of methyl laurate, ethyl laurate, methyl stearate, ethyl stearate, methyl behenate or ethyl behenate, or Several combinations.
  • the normal alkanes are tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, icosane, docosane, trichosan Alkane, tetracosane, pentadecane, and hexadecane.
  • the prepolymerization time in step (1) is 30-60 min, and the prepolymerization temperature is 40-70°C.
  • the reaction time of step (2) is 5-30 min, and the reaction temperature is 40-70°C.
  • the added amount of the polyurethane prepolymer described in step (2) is 4%-20% of the polysiloxane prepolymer, preferably 5%-10%.
  • the mass ratio of the core material and the polyurethane-modified silicone resin prepolymer described in step (3) is 1:1 to 1:6.
  • the concentration of the aqueous solution of the surfactant in step (4) is 1-10%.
  • the emulsification time described in step (5) is 15-60 minutes, the emulsification rate is 1000-10000 rpm, and the emulsification temperature is 50-70°C.
  • the reaction is carried out by heating after adding the catalyst in step (5), and the reaction temperature is 80-95°C.
  • phase-change energy storage microcapsules prepared by the method of the present invention using a polyurethane-modified silicone resin as a shell material.
  • phase-change energy storage microcapsule with a polyurethane-modified silicone resin as a shell material, which includes a shell of the polyurethane-modified silicone resin and a core of the phase-change energy storage material.
  • the silicone resin is polysiloxane.
  • the particle size of the phase change energy storage microcapsules is 500 nm-100um.
  • the ratio of the core material to the shell material is 1:1 to 6:1.
  • phase change energy storage microcapsules directly disperse the core material and shell material in water during the production process, and can directly wash the microcapsules with water in the post-processing, which greatly reduces the production cost, the production process is simple, and the production equipment requirements are low , Easy to industrialize.
  • the silicone resin is a non-combustible material, the flame retardant performance of the phase change energy storage microcapsules is significantly improved.
  • microcapsules prepared by the interfacial polymerization method of the present invention can use cetane, octadecane, eicosane, behenyl, methyl laurate or ethyl laurate, methyl stearate or ethyl stearate. Ester, methyl or ethyl behenate and a combination of two or more of the above are used as the core material, and the polyurethane modified silicone resin is used as the shell material.
  • the phase transition temperature can be based on the phase change energy storage microcapsule
  • the actual use temperature is adjusted so that the phase change temperature of the phase change energy storage microcapsule is adjustable, and the phase change enthalpy value of the phase change energy storage microcapsule is high, which can reach more than 180J/g ( Figure 4).
  • phase change energy storage microcapsules of different particle sizes can be made, and the particle size of phase change energy storage microcapsules can be controlled between 500nm and 100um.
  • Silicone resin has excellent properties such as temperature resistance, flame retardancy and high hardness. However, as the shell material of microcapsules, it has poor film-forming properties, and the shell material of the formed microcapsules is brittle and has poor flexibility. The coverage rate is low. Polyurethane has excellent flexibility, abrasion resistance, adhesion and solvent resistance. The introduction of polyurethane into the silicone resin not only retains the good heat resistance of the silicone resin, but also makes up for the lack of mechanical strength, solvent resistance, poor film formation, poor adhesion, and low coverage of the silicone resin. Can effectively reduce its curing temperature.
  • phase change energy storage microcapsules Polyurethane-modified silicone resin is used as the shell of phase change energy storage microcapsules.
  • the crosslinking density is high and the polymer molecules present a spatial network structure. Therefore, the obtained phase change energy storage microcapsules have a smooth surface and good compactness of the shell (as shown in the figure). 1,2,3), it has a certain strength, so the microcapsule has excellent processability, and its heat resistance (heat resistance can reach more than 200 °C, as shown in Figure 3), as well as excellent thermal oxidation stability, electrical Insulation performance, weather resistance, waterproof, anti-salt spray, anti-mold, biocompatibility and other characteristics.
  • phase change energy storage microcapsules are directly synthesized in water, and the post-treatment is directly washed with water, avoiding the use of a large amount of organic solvents, achieving environmental protection, non-toxicity, and reducing production costs.
  • the production process is simple, the requirements for production equipment are low, and it is easy to scale up experiments for industrialization.
  • the silicone resin is a non-combustible material, the flame retardant performance of the phase change energy storage microcapsules is significantly improved. Therefore, the phase change energy storage microcapsules will have broad application prospects in thermal interface materials.
  • Figure 1 is an ordinary optical microscope photograph of Example 1 of the present invention.
  • Example 2 is a photograph of a polarizing microscope of Example 1 of the present invention.
  • Figure 3 is a scanning electron microscope photograph of Example 1 of the present invention.
  • Figure 4 is a differential scanning calorimetry curve of n-docosane in Example 1 of the present invention.
  • Figure 5 is a differential scanning calorimetry curve of Example 1 of the present invention.
  • Fig. 6 is a thermogravimetric analysis curve of Example 2 of the present invention.
  • the morphology of the microcapsules observed by the optical microscope and the scanning electron microscope was a smooth, compact spherical surface;
  • the melting peak temperature of the microcapsules of Example 1 of the present invention measured by the differential scanning calorimetry method was 45.96°C, and the endothermic enthalpy of melting was 183.4J. /g, the exothermic enthalpy of crystallization is 183.8J/g, which shows that it has a high heat storage capacity; thermogravimetric analysis of the microcapsules of Example 2 of the present invention has good stability below 227.52°C.

Abstract

一种聚氨酯改性有机硅树脂为壳材的相变储能微胶囊及其制备方法，该制备方法包括以下步骤：（1）将生成有机硅树脂的单体混合均匀，加入催化剂进行预聚，获得聚硅氧烷的预聚物；（2）将氨酯预聚体加入到（1）中，反应得到聚氨酯改性有机硅树脂预聚体；（3）芯材与壳材预聚体混合均匀，获得芯材与壳材预聚体混合物；（4）配制表面活性剂的水溶液；（5）将芯材与壳材预聚体混合物和表面活性剂的水溶液进行混合并乳化，获得乳化液，并加入催化剂至反应结束，分离干燥后获得聚氨酯改性有机硅树脂壳相变储能微胶囊。

Description

一种聚氨酯改性有机硅树脂为壳材的相变储能微胶囊及其制备方法 技术领域
本发明属于相变储能技术领域，具体涉及一种聚氨酯改性有机硅树脂为壳材的相变储能微胶囊及其制备方法。
背景技术
相变储能技术就是应用微胶囊技术在固-液相变储能材料微粒表面包覆一层性能稳定的膜而形成具有“核-壳”结构的复合相变储能材料的技术。相变储能材料在应用过程中会出现泄漏、体积变化和易腐蚀的问题，因此需要将相变储能材料进行微胶囊化封装。
相变储能微胶囊的壳材通常可以分为有机壳材和无机壳材，无机类壳材大多是通过无机物前驱体在相变储能材料的表面进行水解-缩合作用实现对相变储能材料的包覆的，但无机壳材的韧性差，在使用过程中容易破裂，实现工业化困难。有机壳材韧性优良，易加工，容易实现产业化。
例如，公开号CN109054768A的专利文献报道石蜡@碳酸钙相变储能微胶囊，该相变储能微胶囊以石蜡为芯材，碳酸钙为壳材。以无机材料碳酸钙为壳材，该相变储能微胶囊存在着壳的韧性差，加工过程中容易破裂，且碳酸钙不耐酸，容易在酸环境中降解，在微胶囊干燥过程中容易出现结块现象，干燥时不能形成粒径均一的粉末。
例如，公开号CN109868116A的专利报道的相变储能微胶囊是以三聚氰胺-甲醛树脂为壳材，从其SEM图可以看出，该微胶囊出现大量的破壳现象，说明壳材的韧性不够，同时该壳材的相变储能微胶囊在生产以及使用过程中有致癌物甲醛的存在，容易造成环境的污染，对操作工人以及使用者将造成身体上的伤害。
发明内容
针对现有相变储能微胶囊的缺点和不足之处，本发明旨在提供一种壳材韧性优良，粒径可控，加工性能优越的聚氨酯改性有机硅树脂壳相变储能微胶囊。该相变储能微胶囊在制备中直接在水相中合成，能够有效降低生产成本，减少环境污染；加工工艺简单，产品对生产者以及使用者不会造成身体伤害。
本发明采用界面聚合法，以聚氨酯改性有机硅脂预聚体为油溶性反应单体，以水为水溶性反应单体，主要反应式如下：
Figure PCTCN2020130865-appb-000001
Figure PCTCN2020130865-appb-000002
Figure PCTCN2020130865-appb-000003
本发明一个方面提供了一种聚氨酯改性有机硅树脂为壳材的相变储能微胶囊的制备方法，其包括如下步骤：
(1)将生成聚硅氧烷的单体混合均匀，加入催化剂进行预聚，获得聚硅氧烷的预聚物；
(2)聚氨酯预聚体加入到聚硅氧烷的预聚物中，反应得到聚氨酯改性有机硅树脂预聚体；
(3)将芯材与聚氨酯改性有机硅树脂预聚体混合均匀，获得芯材与聚氨酯改性有机硅树脂预聚体混合物；
(4)配制表面活性剂的水溶液；
(5)将芯材与聚氨酯改性有机硅树脂预聚体混合物和表面活性剂的水溶液进行混合并乳化，获得乳化液，并加入催化剂至反应结束，分离干燥后获得聚氨酯改性有机硅树脂壳相变储能微胶囊；
其中，所述的芯材为相变储能材料；所述的表面活性剂为水包油型乳化剂。
在本发明的技术方案中，生成聚硅氧烷的单体为乙烯基硅油与氢含量为0.1～2.0的含氢硅油。
在本发明的技术方案中，乙烯基硅油选自甲基乙烯基硅油、苯乙烯基硅油、双乙烯基硅油、四甲基二乙烯基二硅氧烷或多乙烯基硅油，优选四甲基二乙烯基二硅氧烷。
在本发明的技术方案中，氢含量为0.1～2.0的含氢硅油选自聚甲基氢硅氧烷。
在本发明的技术方案中，聚氨酯预聚体为二异氰酸酯单体与聚醚二元醇为原料合成的聚氨酯预聚物，二异氰酸酯单体选自二苯甲烷二异氰酸酯(MDI)，2,4-甲苯二异氰酸酯(TDI)，异佛尔酮二异氰酸酯(IPDI)及其二聚体或多聚体，优选二苯甲烷二异氰酸酯单体，2,4-甲苯二异氰酸酯单体及其二聚体或多聚体。
在本发明的技术方案中，聚氨酯预聚体加入量为聚硅氧烷预聚物的4％-20％，优选5％-10％。
在本发明的技术方案中，乳化剂的HLB值为8-15，更优选地，乳化剂为苯乙烯马来酸酐共聚物钠盐、十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠、OP-10、吐温80、椰油酰胺丙基二甲胺乙内酯、聚氧乙烯(16)失水山梨醇单妥尔油酸酯、聚氧乙烯(10)失水山梨醇单月桂酸酯、聚氧乙烯(20)失水山梨醇二油酸酯、松香酸钠、C14-18烷基硫酸钠、二烷基磺基琥珀酸盐或它们的复配物、PVA。
在本发明的技术方案中，步骤(1)和(5)中的催化剂独立地选自铂催化剂、有机锡催化剂，优选地，有机锡催化剂为二月桂酸二丁基锡、辛酸亚锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡、二乙酸二丁基锡、二氯化二丁基锡、三氯化甲基锡和氯化三甲基锡、二癸酸二丁基锡、异辛酸锌、新癸酸铋，铂催化剂为铂(0)-二乙烯基四甲基二硅氧烷复合物(Karstedt催化剂)。
在本发明的技术方案中，步骤(1)中的催化剂用量为反应单体的0.025～0.1％。
在本发明的技术方案中，步骤(5)中的催化剂用量步骤(1)中催化剂用量的5-20倍。
在本发明的技术方案中，所述芯材选自正烷烃、或油溶性酯类相变材料，
优选地，油溶性酯类相变材料选自月桂酸甲酯、月桂酸乙酯、硬脂酸甲酯、硬脂酸乙酯、山嵛酸甲酯或山嵛酸乙酯中的一种或几种的组合。
优选地，所述的正烷烃为十四烷、十五烷、十六烷、十七烷、十八烷、十九烷、二十烷、二十一烷、二十二烷、二十三烷、二十四烷、二十五烷、二十六烷。
在本发明的技术方案中，步骤(1)预聚时间为30～60min，预聚温度为40～70℃。
在本发明的技术方案中，步骤(2)反应时间为5～30min，反应温度为40～70℃。
在本发明的技术方案中，步骤(2)所述的聚氨酯预聚体加入量为聚硅氧烷预聚物的4％-20％，优选5％-10％。
在本发明的技术方案中，步骤(3)所述的芯材与聚氨酯改性有机硅树脂预聚体的质量比为1:1～1:6。
在本发明的技术方案中，步骤(4)表面活性剂的水溶液的浓度为1～10％。
在本发明的技术方案中，步骤(5)所述的乳化时间15～60min，乳化速率为1000～10000rpm，乳化温度为50～70℃。
在本发明的技术方案中，步骤(5)所述的加入催化剂后加热进行反应，反应温度为80～95℃。
本发明另一个方面提供了本发明所述方法制备得到的聚氨酯改性有机硅树脂为壳材的相变储能微胶囊。
本发明再一个方面提供了聚氨酯改性有机硅树脂为壳材的相变储能微胶囊，其包括聚氨酯改性有机硅树脂的外壳，以及相变储能材料的内核。
在本发明的技术方案中，所述的有机硅树脂为聚硅氧烷。
在本发明的技术方案中，所述相变储能微胶囊的粒径为500nm-100um。
在本发明的技术方案中，芯材与壳材的比例为：1:1～6:1。
该相变储能微胶囊在生产过程中直接将芯材与壳材分散在水中，后期处理中可以直接用水对微胶囊进行洗涤，这就大大降低了生产成本，生产工艺简单，生产设备要求低，易产业化。同时由于有机硅树脂为不可燃材料，显著提高了相变储能微胶囊的阻燃性能。
有益效果
本发明采用界面聚合法制备的微胶囊，可以采用十六烷、十八烷、二十烷、二十二烷、月桂酸甲酯或者月桂酸乙酯、硬脂酸甲酯或硬脂酸乙酯、山嵛酸甲酯或乙酯以及以上两种或两种以上的复配物为芯材，以聚氨酯改性有机硅树脂为壳材，相变温度可以根据该相变储能微胶囊的实际使用温度进行调控，做到相变储能微胶囊的相变温度可调，同时该相变储能微胶囊的相变焓值高，可达到180J/g以上(如图4)。
根据不同的乳化剂、乳化时间以及乳化速率来做不同颗粒尺寸的相变储能微胶囊，可以做到相变储能微胶囊的粒径在500nm～100um之间可控。
有机硅树脂具有耐温性、阻燃性及其高硬度等优异的性能，但作为微胶囊的壳材，成膜性较差，且形成的微胶囊的壳材的较脆，柔韧性差，包覆率低。聚氨酯具有极好的柔韧性、耐磨性、粘结性、耐溶剂性。将聚氨酯引入有机硅树脂中，即保留了有机硅树脂良好的耐热性，又能弥补有机硅树脂的力学强度、耐溶剂性、成膜性差、附着力差、包覆率低的不足，并能有效地降低其固化温度。
聚氨酯改性有机硅树脂作为相变储能微胶囊的壳，交联密度大，聚合物分子呈现空间网状结构，因此得到的相变储能微胶囊表面光滑，壳的致密性良好(如图1,2,3)，具有一定的强度因而该微胶囊具有优良的可加工性能，及其耐热性(可耐热达到200℃以上，如图3)，以及优异的热氧化稳定性、电绝缘性能、耐候性、防水、防盐雾、防霉菌、生物相容性等特性。
该相变储能微胶囊直接在水中合成，后期处理直接用水进行洗涤，避免了大量有机溶剂的使用，做到了环保无毒且降低了生产成本。生产工艺简单，对生产设备要求低，容易放大实验进行产业化。同时由于有机硅树脂为不可燃材料，显著提高了相变储能微胶囊的阻燃性能。因此该相变储能微胶囊在热界面材料中将有广阔的应用前景。
附图说明
图1是本发明实施例1的普通光学显微镜照片图；
图2是本发明实施例1的偏光显微镜照片图；
图3是本发明实施例1的扫描电子显微镜照片图；
图4是本发明实施例1正二十二烷的差示扫描量热法曲线；
图5是本发明实施例1的差示扫描量热法曲线；
图6是本发明实施例2的热重分析曲线。
具体实施方式
为了使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明，但不能理解为对本发明的可实施范围的限定。
其是通过以下步骤制备的：
实施例1有聚氨酯改性机硅树脂为壳材的相变储能微胶囊的制备
(1)聚硅氧烷预聚物的制备，将反应单体四甲基二乙烯基二硅氧烷和聚甲基氢硅氧烷混合均匀，加入单体质量的0.025％的催化剂铂(0)-二乙烯基四甲基二硅氧烷复合物，在温度为60℃的水浴中预聚45min制备聚硅氧烷预聚物20克。
(2)壳材预聚体的制备，将1克聚氨酯聚预体加入到(1)中，恒温60℃搅拌15分钟，得到聚氨酯改性有机硅树脂预聚体。
(3)称取质量分数为4:1的芯材月桂酸乙酯与壳材预聚体混合均匀备用。
(4)称取含有2％的表面活性剂为SDS的水溶液200mL。
(5)将(3)加入(4)进行乳化，搅拌速率为6000rpm，乳化温度为60℃，乳化时间为35min。
(6)乳化结束，降低转速，加入单体质量的0.5％的催化剂二月桂酸二丁基锡，升温至80℃，继续反应4小时结束反应，用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5～8小时得到聚氨酯改性有机硅树脂壳相变储能微胶囊粉末。
实施例2聚氨酯改性有机硅树脂为壳材的相变储能微胶囊的制备
(1)聚硅氧烷预聚物的制备，将反应单体四甲基二乙烯基二硅氧烷和聚甲基氢硅氧烷混合均匀，加入单体质量的0.03％的催化剂铂(0)-二乙烯基四甲基二硅氧烷复合物，在温度为55℃的水浴中预聚40min制备成聚硅氧烷预聚物16克。
(2)壳材预聚体的制备，将0.8克聚氨酯预聚体加入(1)中搅拌混匀，恒温60℃搅拌15分钟，得到聚氨酯改性有机硅树脂预聚体。
(3)称取质量分数为4.5:1的芯材山嵛酸甲酯与壳材预聚体混合均匀备用。
(4)称取含有2％的表面活性剂为SDS的水溶液200mL。
(5)将(3)加入(4)进行乳化，搅拌速率为1500rpm，乳化温度为65℃，乳化45min。
(6)乳化结束，降低转速，再次加入单体质量的0.4％的催化剂铂(0)-二乙烯基四甲基二硅氧烷复合物，升温至85℃，继续反应5小时结束反应，用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5～8小时得到粒径为10μm～40μm(平均粒径为30μm)聚氨酯改性有机硅树脂壳相变储能微胶囊粉末。
实施例3聚氨酯改性有机硅树脂为壳材的相变储能微胶囊的制备
(1)聚硅氧烷预聚物的制备，将反应单体四甲基二乙烯基二硅氧烷和聚甲基氢硅氧烷按某一比例混合均匀，加入单体质量的0.05％的二月桂酸二丁基锡在温度为70℃的水浴中预聚35min制备成聚硅氧烷预聚物30克。
(2)壳材预聚体的制备，将2克聚氨酯预聚体加入(1)中搅拌混匀，恒温60℃搅拌15分钟，得到聚氨酯改性有机硅树脂预聚体。
(3)称取质量分数为5:1的芯材正十八烷与壳材预聚体混合均匀备用。
(4)称取含有7％的表面活性剂为PVA的水溶液200mL。
(5)将(3)加入(4)进行乳化，搅拌速率为8000rpm，乳化温度为70℃，乳化25min。
(6)乳化结束，降低转速，加入单体质量的0.5％的催化剂二月桂酸二丁基锡，升温至90℃，继续反应3小时结束反应，用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5～8小时得到粒径为300nm～1.0μm(平均粒径为800nm)聚氨酯改性有机硅树脂壳相变储能微胶囊粉末。
实施例4聚氨酯改性有机硅树脂为壳材的相变储能微胶囊的制备
(1)聚硅氧烷预聚物的制备，将反应单体四甲基二乙烯基二硅氧烷和聚甲基氢硅氧烷，按1:1的比例混合，加入单体质量的0.03％的催化剂铂(0)-二乙烯基四甲基二硅氧烷复合物，在温度为45℃的水浴中预聚15min制备完成聚硅氧烷预聚物16克。
(2)壳材预聚体的制备，将4克聚氨酯聚预体加入到(1)中，恒温60℃搅拌15分钟，得到聚氨酯改性有机硅树脂预聚体。
(3)称取质量分数为6:1的芯材硬脂酸甲酯和正二十烷混合物与壳材预聚体混合均匀备用。
(4)称取含有10％的表面活性剂为SMA的水溶液300mL(pH值：4.0～5.0)。
(5)将(3)加入(4)进行乳化，搅拌速率为3000rpm，乳化温度为70℃，乳化25min。
(6)乳化结束，降低转速，加入单体质量的0.3％的催化剂铂(0)-二乙烯基四甲基二硅氧烷复合物，升温至95℃，继续反应5小时结束反应，用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5～8小时得到粒径为5μm～22μm(平均粒径为18μm)聚氨酯改性有机硅树脂壳相变储能微胶囊粉末。
效果例
光学显微镜和扫描电子显微镜观察微胶囊的形貌为表面光滑、致密的球形；差示扫描量热法测定本发明实施例1的微胶囊的熔化峰温度为45.96℃，熔化吸热焓为183.4J/g，结晶放热焓为183.8J/g，显示其具有较高的热储存能力；热重法分析本发明实施例2在227.52℃以下微胶囊具有良好的稳定性。

Claims (10)

  1. 一种聚氨酯改性有机硅树脂为壳材的相变储能微胶囊的制备方法，其包括如下步骤：
    (1)将生成聚硅氧烷的单体混合均匀，加入催化剂进行预聚，获得聚硅氧烷的预聚物；
    (2)将氨酯预聚体加入到聚硅氧烷的预聚物中，反应得到聚氨酯改性有机硅树脂预聚体；
    (3)将芯材与聚氨酯改性有机硅树脂预聚体混合均匀，获得芯材与聚氨酯改性有机硅树脂预聚体混合物；
    (4)配制表面活性剂的水溶液；
    (5)将芯材与聚氨酯改性有机硅树脂预聚体混合物和表面活性剂的水溶液进行混合并乳化，获得乳化液，并加入催化剂至反应结束，分离干燥后获得聚氨酯改性有机硅树脂壳相变储能微胶囊；
    其中，所述的芯材为相变储能材料；所述的表面活性剂为水包油型乳化剂。
  2. 根据权利要求1所述的制备方法，其中生成有聚硅氧烷的单体为乙烯基硅油与氢含量为0.1～2.0的含氢硅油；
    优选地，乙烯基硅油选自甲基乙烯基硅油、苯乙烯基硅油、双乙烯基硅油、四甲基二乙烯基二硅氧烷或多乙烯基硅油，优选四甲基二乙烯基二硅氧烷；
    优选地，氢含量为0.1～2.0的含氢硅油，优选聚甲基氢硅氧烷。
  3. 根据权利要求1所述的制备方法，其中，聚氨酯预聚体为二异氰酸酯单体与聚醚二元醇为原料合成的聚氨酯预聚物，二异氰酸酯单体选自二苯甲烷二异氰酸酯(MDI)，2,4-甲苯二异氰酸酯(TDI)，异佛尔酮二异氰酸酯(IPDI)及其二聚体或多聚体，优选二苯甲烷二异氰酸酯单体，2,4-甲苯二异氰酸酯单体及其二聚体或多聚体；
    更优选地，聚氨酯预聚体加入量为聚硅氧烷预聚物的4％-20％。
  4. 根据权利要求1所述的制备方法，其中，乳化剂的HLB值为8-15，优选地，乳化剂为苯乙烯马来酸酐共聚物钠盐、十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠、OP-10、吐温80、椰油酰胺丙基二甲胺乙内酯、聚氧乙烯(16)失水山梨醇单妥尔油酸酯、聚氧乙烯(10)失水山梨醇单月桂酸酯、聚氧乙烯(20)失水山梨醇二油酸酯、松香酸钠、C14-18烷基硫酸钠、二烷基磺基琥珀酸盐或它们的复配物、PVA。
  5. 根据权利要求1所述的制备方法，其中，步骤(1)和(5)中的催化剂独立地选自铂 催化剂、有机锡催化剂；
    优选地，步骤(1)中的催化剂用量为反应单体质量的0.025～0.1％；
    优选地，步骤(5)中的催化剂用量步骤(1)中催化剂用量的5-20倍。
  6. 根据权利要求1所述的制备方法，其中，所述相变储能材料选自正烷烃、或油性酯类相变材料中的一种或多种的组合，
    优选地，油性酯类相变材料选自月桂酸甲酯、月桂酸乙酯、硬脂酸甲酯、硬脂酸乙酯、山嵛酸甲酯或山嵛酸乙酯，
    优选地，正烷烃选自十四烷、十五烷、十六烷、十七烷、十八烷、十九烷、二十烷、二十一烷、二十二烷、二十三烷、二十四烷、二十五烷或二十六烷。
  7. 根据权利要求1所述的制备方法，其中，步骤(1)预聚的反应温度为40～70℃；步骤(2)反应时间为5～30min，反应温度为40～70℃；步骤(5)所述的加入催化剂后加热进行反应，反应温度为80～95℃。
  8. 根据权利要求1所述的制备方法，其中，在本发明的技术方案中，步骤(3)所述的芯材与聚氨酯改性有机硅树脂预聚体的质量比为1:1～1:6。
  9. 根据权利要求1-8任一项所述的制备方法制备获得的聚氨酯改性有机硅树脂为壳材的相变储能微胶囊。
  10. 聚氨酯改性有机硅树脂为壳材的相变储能微胶囊，其包括聚氨酯改性有机硅树脂的外壳，以及相变储能材料的内核；
    优选地，所述的有机硅树脂为聚硅氧烷；
    优选地，所述相变储能微胶囊的粒径为500nm-100um；
    优选地，芯材与壳材的比例为：1:1～6:1。
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