WO2021098656A1 - 一种有机硅氮烷聚合物树脂为壳材的相变储能微胶囊及其制备方法 - Google Patents

一种有机硅氮烷聚合物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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WO2021098656A1
WO2021098656A1 PCT/CN2020/129170 CN2020129170W WO2021098656A1 WO 2021098656 A1 WO2021098656 A1 WO 2021098656A1 CN 2020129170 W CN2020129170 W CN 2020129170W WO 2021098656 A1 WO2021098656 A1 WO 2021098656A1
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energy storage
change energy
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phase change
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刘海生
喻学锋
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Shenzhen Institute of Advanced Technology of CAS
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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
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation

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  • the invention belongs to the technical field of phase change energy storage materials, and specifically relates to a phase change energy storage microcapsule with an organosilazane polymer resin as a shell material and a preparation method thereof.
  • the interfacial polymerization method is to dissolve two monomers or polymers with different hydrophilicity and hydrophobicity in the water phase and the organic phase (oil phase) that are immiscible with each other.
  • the solution of one phase is dispersed into the solution of the other phase (emulsification)
  • Interfacial polymerization has the advantages of fast reaction speed, mild conditions, and lower requirements for monomer purity and ratio.
  • phase change energy storage microcapsules prepared by the interfacial polymerization method published in the prior patent technology have thin shell materials, poor compactness, poor mechanical strength and thermal stability, and are not suitable for coating phase change energy storage materials that require good airtightness .
  • the tightness of the microcapsule is closely related to the structure of the shell material.
  • Organosilazane polymer is a type of organic polymer with Si-NH-Si as the main chain. Due to its special chemical structure, the organosilazane polymer has excellent film-forming properties and can be polymerized and cured to form an ultra-thin, dense Microcapsule shell material with excellent heat resistance, heat resistance and mechanical strength.
  • the organic silazane polymer can be cured at room temperature.
  • the main reaction is the hydrolysis and oxidation of the Si-NH-Si bond.
  • the barrier coatings made from them are often applied to OLED displays, organic solar photovoltaics and quantum materials, etc.
  • a high-quality ultra-thin film is formed on the surface of various components, which can isolate moisture and oxygen, and has an unparalleled protective effect on these components.
  • Organic silazane polymer resin also has excellent flexibility, resistance to organic solvents, flame retardancy (non-flammable), light transmittance (visible light transmittance: >90%), UV resistance and other properties.
  • the present invention uses organosilazane polymer resin as the shell material of phase change energy storage microcapsules, and uses normal alkane phase change material as the core material of phase change energy storage microcapsules, and adopts interfacial polymerization.
  • the phase change energy storage microcapsules with organosilazane polymer resin as the shell material are prepared by the method.
  • the shell material is ultra-thin, has good compactness, mechanical strength and thermal stability, controllable particle size, and high phase change latent heat value.
  • Thermal interface materials for devices, textiles and clothing, solar energy storage and other industries have broad application prospects.
  • the present invention adopts the following technical solutions.
  • the organosilazane polymer resin is used as the shell material in phase change energy storage microcapsules, and the phase change energy storage microcapsules prepared by the interfacial polymerization method can maintain the compactness of the microcapsules under the premise of ultra-thin shell materials.
  • Mechanical strength, heat resistance and other excellent properties make up for the shortcomings of the phase change energy storage microcapsules prepared by the interfacial polymerization method published by the existing patent technology, and have important application value.
  • One aspect of the present invention provides a method for preparing phase change energy storage microcapsules with organosilazane polymer resin as a shell material, which includes the following steps:
  • the temperature of the emulsion is raised to 55-75°C, a catalyst is added, and the temperature is raised to 80-95°C to obtain a phase change energy storage microcapsule with an organosilazane polymer resin shell.
  • the emulsifier is selected from oil-in-water emulsifiers, preferably the emulsifier has an HLB value of 8-15. More preferably, the emulsifier is styrene maleic anhydride copolymer sodium salt, ten Sodium dialkylbenzene sulfonate, sodium lauryl sulfonate, sodium lauryl sulfate, OP-10, Tween 80, cocamidopropyl dimethylamine hydantoin, polyoxyethylene (16) Sorbitan monotalloleate, polyoxyethylene (10) sorbitan monolaurate, polyoxyethylene (20) sorbitan dioleate, sodium rosinate, C14-18 alkyl sulfuric acid Sodium, dialkyl sulfosuccinate or their combination.
  • the concentration of the emulsifier in the water phase in the step 1) is 1-10%, preferably 2.5%-6.0%, more preferably 4%-5%.
  • the ratio of the silazane polymer and the phase change energy storage material in the step 2) is 1:2-1:5, preferably 1:2.8-1:4.5.
  • the phase change energy storage material is selected from one or more of normal alkanes.
  • the normal alkanes are tetradecane, pentadecane, hexadecane, heptadecane, Octadecane, nonadecane, eicosan, icosane, docosane, tricosane, tetracosane, pentadecane, hexadecane.
  • the organic solvent in step 2) is selected from organic solvents that can dissolve silazane polymer, preferably ethyl acetate, butyl acetate, acetone, cyclohexanone, toluene, xylene .
  • the catalysts in the steps 2) and 3) are selected from platinum(0)-divinyltetramethyldisiloxane complexes and organotin catalysts.
  • the organotin catalyst is Dibutyl tin dilaurate, stannous octoate, di(dodecyl sulfide) dibutyl tin, dibutyl tin diacetate, dibutyl tin diacetate, dibutyl tin dichloride, methyl tin trichloride and trimethyl tin chloride , Dibutyltin Didecanoate, Zinc Isooctanoate, Bismuth Neodecanoate.
  • step 2) is mixed at a temperature at which the phase change energy storage material melts, preferably 20-50°C.
  • step 3) is to heat the water phase at 55-75°C for 5-30 minutes, add the oil phase to the water phase, and disperse at high speed to form a stable oil-in-water emulsion;
  • Another aspect of the present invention provides phase change energy storage microcapsules in which the organosilazane polymer resin prepared by the method of the present invention is a shell material.
  • phase change energy storage microcapsule with organosilazane polymer resin as the shell material which includes a shell of the silazane polymer and a core of the phase change energy storage material.
  • the energy storage material is n-alkane; the mass ratio of the silazane polymer to the phase change energy storage material is 1:2-1:5.
  • the normal alkanes are tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, icosane, docosane, trichosan Alkane, tetracosane, pentadecane, and hexadecane.
  • the mass ratio of the silazane polymer to the phase change energy storage material is 1:2.8-1:4.5.
  • the particle size of the phase change energy storage microcapsules is 300 nm-100 ⁇ m.
  • phase change energy storage microcapsule with the organosilazane polymer resin as the shell material of the present invention includes:
  • the interfacial polymerization method is to dissolve two monomers or polymers with different hydrophilicity and hydrophobicity in the water phase and the organic phase (oil phase) that are immiscible with each other.
  • Interfacial polymerization has the advantages of fast reaction speed, mild conditions, and lower requirements for monomer purity and ratio.
  • water is used as the water-soluble reaction monomer
  • the organosilazane polymer is used as the oil-soluble reaction monomer.
  • the main reaction is the hydrolysis and oxidation of the Si-NH-Si bond of the organosilazane polymer. Promote the reaction of Si-H and Si-NH-Si, and form an ultra-thin and super-hard organosilazane polymer resin shell material with a three-dimensional cross-linked structure after curing.
  • the present invention uses organosilazane polymer resin as the shell material, and n-alkane phase-change energy storage material as the core material, and uses the interfacial polymerization method to prepare a phase-change energy storage microstructure with an ultra-thin organosilazane polymer resin shell. capsule.
  • the water phase is the emulsifier aqueous solution and deionized water
  • the oil phase is the mixture of organosilazane polymer, ethyl acetate and phase change energy storage material.
  • the water phase and oil phase are mixed and dispersed at high speed to form an emulsion.
  • the organosilazane polymer undergoes hydrolysis, oxidation and polycondensation addition reaction at the water-oil interface to form an organosilazane polymer resin shell, which coats the phase change energy storage material In it.
  • the technical problem to be solved by the present invention is to provide a phase change energy storage microcapsule with an organosilazane polymer resin as a shell material and a preparation method thereof.
  • the present invention uses an interfacial polymerization method to prepare the organosilazane polymer resin It is a phase change energy storage microcapsule of shell material. Under the premise of ultra-thin shell material, it can also maintain the excellent performance of microcapsules such as compactness, mechanical strength and heat resistance.
  • This phase change energy storage microcapsule solves the existing problems.
  • the phase change energy storage microcapsules prepared by the interfacial polymerization method published by the patent technology have the problems of compactness, poor mechanical strength and thermal stability.
  • the preparation method of the present invention has mild conditions, simple and easy-to-control process, and the prepared phase change material microcapsules have good sealing performance, high mechanical strength, high heat resistance and heat storage performance, good stability, and flexibility , Organic solvent resistance, flame retardancy (non-flammable), light transmittance (visible light transmittance: >90%), UV resistance and other excellent properties.
  • 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 an ordinary optical microscope photograph of Example 2 of the present invention.
  • Figure 4 is a scanning electron microscope photograph of Example 1 of the present invention.
  • Fig. 5 is a differential scanning calorimetry curve of n-docosane in Example 1 of the present invention.
  • Figure 6 is a differential scanning calorimetry curve of Example 1 of the present invention.
  • Fig. 7 is a thermogravimetric analysis curve of Example 1 of the present invention.
  • FIG. 8 is a scanning electron microscope image of a phase change microcapsule sample prepared by a commercially available interfacial polymerization method with a polyurea resin as a shell material after 15 minutes of ultrasonic vibration.
  • Fig. 9 is a scanning electron micrograph of a sample of phase change microcapsules prepared by the interfacial polymerization method of the present invention with polysilazane as the shell material after ultrasonic oscillation for 30 minutes.
  • the organosilazane polymer is organosilicon polysilazane OPSZ-9150 produced by Anhui Iyota Silicone Oil Co., Ltd.
  • the slurry is diluted with an appropriate amount of deionized water, left to stand and aged for 48 hours, and then washed with deionized water , Filtered under reduced pressure to obtain the filter cake, which is dried in an oven at 70°C for 5-8 hours to obtain a phase change storage of the organosilazane polymer resin with a particle size of 14-30 ⁇ m (average particle size of 26 ⁇ m) as the shell material.
  • the shell phase change energy storage microcapsule slurry is diluted with an appropriate amount of deionized water, and after standing and aging for 48 hours, it is washed with deionized water and filtered under reduced pressure to obtain a filter cake, which is placed in an oven at 70°C Dry for 5-8 hours to obtain phase change energy storage microcapsule powder with a particle size of 900nm-2.4 ⁇ m (average particle size of 1.5 ⁇ m) organosilazane polymer resin as the shell material.
  • the slurry is diluted with an appropriate amount of deionized water, left to stand and aged for 48 hours, and then washed with deionized water , Filtered under reduced pressure to obtain the filter cake, placed in an oven at 70°C for 5-8 hours to obtain a phase change energy storage microcapsule with a shell material of 240nm ⁇ 560nm (average particle size of 510nm) organosilazane polymer resin powder.
  • phase change energy storage microcapsule slurry of the resin shell the slurry is diluted with an appropriate amount of deionized water, and after standing and aging for 48 hours, it is washed with deionized water and filtered under reduced pressure to obtain a filter cake, which is placed at 70°C Dry in an oven for 5-8 hours to obtain phase-change energy storage microcapsule powder with 570nm-860nm (average particle size of 774nm) organosilazane polymer resin as the shell material.
  • the slurry is diluted with an appropriate amount of deionized water, left to stand and aged for 48 hours, and then washed with deionized water , Filtered under reduced pressure to obtain the filter cake, placed in an oven at 70°C for 5 to 8 hours to obtain a particle size of 480nm ⁇ 2.0 ⁇ m (average particle size of 1.1 ⁇ m) organosilazane polymer resin as the shell material phase Variable energy storage microcapsule powder.
  • 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 44.56°C, and the endothermic enthalpy of melting was 200.0J. /g, the exothermic enthalpy of crystallization is 194.9J/g, which shows that it has a high heat storage capacity; thermogravimetric analysis of the microcapsules of Example 1 of the present invention has good stability below 237.73°C.
  • the ultrasonic oscillator is used to generate high-frequency mechanical oscillations, and ultrasonic waves are formed in the medium.
  • the positive and negative high-frequency alternating changes in the medium radiate forward in dense and dense phases, so that countless small bubbles are continuously produced in the medium and burst.
  • the so-called "cavitation effect” produces a series of explosions that release huge energy, forming a huge impact on the surroundings, and continuously impacting the surface of the microcapsule shell material, causing the microcapsules with weaker mechanical strength to rupture.
  • samples are taken at regular intervals for scanning electron microscopy to observe the damage of the microcapsule samples to achieve the purpose of testing the mechanical strength of the microcapsules.
  • Figure 8 is a sample of phase change microcapsules prepared by a commercially available interfacial polymerization method with polyurea resin as a shell material. After 15 minutes of ultrasonic vibration, the scanning electron microscope image of the sample was observed. More than 50% of the microcapsules were observed. The microcapsules burst.
  • Figure 9 is a SEM image of a phase-change microcapsule sample (Example 5 of the present invention) prepared by the interfacial polymerization method of the patent application with a shell material of the organosilazane polymer resin after 30 minutes of ultrasonic oscillation. , Almost no rupture of the microcapsules was observed.
  • the polyurea resin shell material and the organosilazane polymer resin shell material of the microcapsules are insoluble in absolute ethanol, while the core material of the microcapsules, n-docosane, is soluble in ethanol and insoluble in water. Soak a certain amount of microcapsule samples in absolute ethanol, mechanically stir for 15 minutes, then add twice the ethanol water, continue to stir for 15 minutes, then stand for stratification, collect the upper microcapsule slurry and spread it on the absorbent paper After drying for 2 hours at 70°C in an oven, take out the sample, blow off the microcapsule powder of the oil-absorbing paper with an ear ball, and observe the oil stains on the surface of the oil-absorbing paper.
  • the core material n-docosane of the microcapsules with cracks and pore shells is dissolved by absolute ethanol. After adding water, the microcapsules with a lighter specific gravity and the dissolved core material n-docosane float on On the upper layer of the alcohol solution, the core material n-docosane dissolved out will melt into oil at 70°C, and stick to the oil-absorbing paper to form oil stains, so as to detect the sealing performance of the microcapsules.
  • n-docosane is the core material of the phase change microcapsule sample, tested according to the above-mentioned microcapsule sealing performance test method, and observe There is oil stains on the surface of the absorbent paper.
  • the microcapsule sample after 15 minutes of ultrasonic vibration was tested according to the above-mentioned microcapsule sealing performance test method, and it was observed that the entire surface of the oil-absorbing paper was densely covered with oil stains.
  • the polyurea resin prepared by the commercially available interfacial polymerization method is the shell material, and the phase change microcapsule samples with n-docosane as the core material have poor sealing performance, and some microcapsule shell materials have cracks or pores and other damage.
  • the organosilazane polymer resin prepared by the interfacial polymerization method of this patent is the shell material, and the phase change microcapsule sample with n-docosane as the core material has excellent sealing performance, and there are almost no cracks or pores in the microcapsule shell material. And other damage.

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Abstract

本发明涉及一种有机硅氮烷聚合物树脂为壳材的相变储能微胶囊及其制备方法，具体公开了，制备方法包括如下步骤：1）配制水相：配制乳化剂的水溶液，得到水相；2）配制油相：硅氮烷聚合物、有机溶剂、相变储能材料以及催化剂混合均匀得到油相；3）制备乳液：将水相和油相混合，并通过机械分散获得水包油型乳液；4）在使乳液升温至55～75℃，加入催化剂，升温至80～95℃恒温至获得有机硅氮烷聚合物树脂壳的相变储能微胶囊。该相变材料微胶囊具有密封性好、机械强度高、耐热性及储热性能高、稳定性好，并且具有柔韧性、耐有机溶剂性、阻燃性（不可燃）、透光性、抗紫外线等优异的性能。

Description

一种有机硅氮烷聚合物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材料技术领域，具体涉及一种有机硅氮烷聚合物树脂为壳材的相变储能微胶囊及其制备方法。
 背景技术
界面聚合法是将两种亲疏水性不同的单体或聚合物分别溶解在互不相溶的水相和有机相（油相）中，当一相溶液被分散到另一相溶液（乳化）后，两相溶液中的单体在油水界面处发生聚合反应来制备微胶囊的一种方法。界面聚合具有反应速度快、条件温和、对单体纯度和配比要求较低等优点。
现有专利技术公布的界面聚合法制备的相变储能微胶囊壳材较薄，致密性不好，机械强度及热稳定性较差，不适合包覆要求密闭性良好的相变储能材料。微胶囊的密封性跟壳材结构紧密相关。有机硅氮烷聚合物是一类以Si-NH-Si为主链的有机聚合物，由于其特殊的化学结构，使得有机硅氮烷聚合物成膜性优良，可聚合固化形成超薄、致密性、耐热性及机械强度优良的微胶囊壳材。有机硅氮烷聚合物可室温固化，固化过程中，主要反应为Si-NH-Si键的水解和氧化，常用其制成的阻隔性涂料涂布于OLED显示屏、有机太阳能光伏和量子材料等各种组件表面而形成高质量的超薄膜材，能够隔离水分和氧气，对这些组件起到无与伦比的保护效果。有机硅氮烷聚合物树脂，还具有优良的柔韧性、耐有机溶剂性、阻燃性（不可燃）、透光性（可见光透过率：>90%）、抗紫外线等性能。
 技术问题
为了克服现有技术的缺陷，本发明以有机硅氮烷聚合物树脂为相变储能微胶囊的壳材，以正烷烃类相变材料为相变储能微胶囊的芯材，采用界面聚合法制备得到有机硅氮烷聚合物树脂为壳材的相变储能微胶囊，壳材超薄，致密性、机械强度及热稳定性好，粒径可控，相变潜热值高，在电子器件热界面材料、纺织服装、太阳能储能等行业领域具有广阔的应用前景。为了实现上述发明目的，本发明采取了以下技术方案。将有机硅氮烷聚合物树脂作为壳材应用于相变储能微胶囊，利用界面聚合法制备的相变储能微胶囊，在壳材超薄的前提下，还能保持微胶囊的致密性、机械强度及耐热性等优异性能，弥补了现有专利技术公布的界面聚合法所制备的相变储能微胶囊的不足，具有重要应用价值。
 技术解决方案
本发明一个方面提供了一种机硅氮烷聚合物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）配制水相：配制乳化剂的水溶液，得到水相；
2）配制油相：硅氮烷聚合物、有机溶剂、相变储能材料以及催化剂混合均匀得到油相；
3）制备乳液：将水相和油相混合，并通过机械分散获得水包油型乳液；
4）在使乳液升温至55～75℃，加入催化剂，升温至80～95℃恒温至获得有机硅氮烷聚合物树脂壳的相变储能微胶囊。
在本发明的技术方案中，所述的乳化剂选自水包油型乳化剂，优选乳化剂的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。
在本发明的技术方案中，所述的步骤1）中水相中乳化剂的浓度为1-10%，优选为2.5%-6.0%，更优选为4%-5%。
在本发明的技术方案中，所述的步骤2）中硅氮烷聚合物和相变储能材料的配比为1:2-1:5，优选为1:2.8-1:4.5。
在本发明的技术方案中，相变储能材料选自正烷烃中的一种或几种，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，所述的步骤2）中有机溶剂选自能溶解硅氮烷聚合物的有机溶剂，优选为乙酸乙酯、乙酸丁酯、丙酮、环己酮、甲苯、二甲苯。
在本发明的技术方案中，所述的步骤2）和3）中催化剂选自铂（0）-二乙烯基四甲基二硅氧烷复合物、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。
在本发明的技术方案中，所述的步骤2）中催化剂加入量为硅氮烷聚合物：催化剂=1:0.001-0.005，优选为1:0.001-0.003。
在本发明的技术方案中，所述的步骤3）中催化剂加入量为硅氮烷聚合物：催化剂=1:0.002-0.01，优选为1:0.002-0.006。
在本发明的技术方案中，步骤2）在相变储能材料融化的温度下混合，优选为20～50℃。
在本发明的技术方案中，步骤3）为将水相在55～75℃下保温5～30分钟，将油相加入到水相中，高速分散形成稳定的水包油型乳液；
本发明另一个方面提供了本发明所述方法制备得到的机硅氮烷聚合物树脂为壳材的相变储能微胶囊。
本发明再一个方面提供了一种机硅氮烷聚合物树脂为壳材的相变储能微胶囊，其包括硅氮烷聚合物的外壳，以及相变储能材料的内核，所述相变储能材料为正烷烃；所述硅氮烷聚合物与相变储能材料的质量比为1:2-1:5。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，所述的硅氮烷聚合物与相变储能材料的质量比为1:2.8-1:4.5。
在本发明的技术方案中，所述相变储能微胶囊的粒径为300nm-100μm。
本发明的一种有机硅氮烷聚合物树脂为壳材的相变储能微胶囊，包括：
（1）配制水相；将4.0～65.0克乳化剂或乳化剂水溶液和10.0～75.0克去离子混匀，得到水相；
（2）将5.0～15.0克有机硅氮烷聚合物和10.0～40.0克乙酸乙酯混合，搅拌至完全互溶后，加入5.0～60.0克相变储能材料，在20～50℃条件下完全互溶，再添加0.025～1.0克催化剂，搅拌混匀，制得油相；
（3）将水相在55～75℃下保温5～30分钟，将油相加入到水相中，1000～10000rpm高速分散5～30分钟，形成稳定的水包油型乳液；
（4）将向上述乳液，在55～75℃下保温15～30分钟后，再次滴加0.05～1.5克催化剂，升温至80～95℃恒温2.0～6.0小时，即得具有超薄的有机硅氮烷聚合物树脂壳的相变储能微胶囊。
本发明所应用的界面聚合法原理如下：
界面聚合法是将两种亲疏水性不同的单体或聚合物分别溶解在互不相溶的水相和有机相（油相）中，当一相溶液被分散到另一相溶液（乳化）后，两相溶液中的单体在油水界面处发生聚合反应来制备微胶囊的一种方法。界面聚合具有反应速度快、条件温和、对单体纯度和配比要求较低等优点。本发明以水作为水溶性反应单体，以有机硅氮烷聚合物作为油溶性反应单体，主要反应为有机硅氮烷聚合物Si-NH-Si键的水解和氧化，添加适当催化剂又可以促进Si-H和Si-NH-Si的反应，固化之后形成三维交联结构的超薄超硬有机硅氮烷聚合物树脂壳材。
本发明以有机硅氮烷聚合物树脂作为壳材，以正烷烃类相变储能材料作为芯材，利用界面聚合法制备具有超薄的有机硅氮烷聚合物树脂壳的相变储能微胶囊。其中水相是乳化剂水溶液以及去离子水，油相是有机硅氮烷聚合物、乙酸乙酯和相变储能材料混合物。水相、油相混合后高速分散形成乳液，有机硅氮烷聚合物在水油界面上发生水解和氧化以及缩聚加成反应形成有机硅氮烷聚合物树脂外壳，将相变储能材料包覆在其中。
 有益效果
（1）本发明所要解决的技术问题是提供一种有机硅氮烷聚合物树脂为壳材的相变储能微胶囊及其制备方法，本发明利用界面聚合法制备有机硅氮烷聚合物树脂为壳材的相变储能微胶囊，在壳材超薄的前提下，还能保持微胶囊的致密性、机械强度及耐热性等优异性能，该相变储能微胶囊解决了现有专利技术公布的界面聚合法所制备的相变储能微胶囊存在致密性，机械强度及热稳定性较差的问题。
（2）本发明的制备方法条件温和，工艺简单易控，制备出的相变材料微胶囊具有密封性好、机械强度高、耐热性及储热性能高、稳定性好，并且具有柔韧性、耐有机溶剂性、阻燃性（不可燃）、透光性（可见光透过率：>90%）、抗紫外线等优异的性能。
 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2的普通光学显微镜照片图；
图4是本发明实施例1的扫描电子显微镜照片图；
图5是本发明实施例1正二十二烷的差示扫描量热法曲线；
图6是本发明实施例1的差示扫描量热法曲线；
图7是本发明实施例1的热重分析曲线。
图8为市售的界面聚合法制备的聚脲树脂为壳材的相变微胶囊样品在超声振荡15分钟后，取样的扫描电镜图。
图9为本发明界面聚合法制备的聚硅氮烷为壳材的相变微胶囊样品在超声振荡30分钟后，取样的扫描电镜图。
 本发明的最佳实施方式
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。
本发明中，所述机硅氮烷聚合物为安徽艾约塔硅油有限公司生产的有机硅聚硅氮烷OPSZ-9150。
实施例1有机硅氮烷聚合物树脂为壳材的相变储能微胶囊的制备
（1）水相的配制
称取60克10%苯乙烯马来酸酐共聚物钠盐(SMA-Na)水溶液于烧杯中，加去离子水至100克，搅拌，使乳化剂完全溶解，用冰醋酸调节pH：4.0～5.0，配制成5%的乳化剂水溶液，得到水相；
（2）油相的配制
在烧杯中加入14克有机硅氮烷聚合物和40克乙酸乙酯混合，搅拌至完全互溶后，加入60克正二十二烷，在20～30℃条件下完全互溶，再添加0.025克铂（0）-二乙烯基四甲基二硅氧烷复合物，搅拌混匀，制得油相；
（3）乳液的形成
将水相在70℃下保温10分钟后，将油相加入到水相中，2000rpm高速分散15分钟，形成稳定的水包油型乳液；
（4）微胶囊的形成
乳化结束，降低转速，向上述乳液加入0.05克的铂（0）-二乙烯基四甲基二硅氧烷复合物，在70℃下保温30分钟后，升温至85℃，继续反应4小时结束反应，得到具有超薄的有机硅氮烷聚合物树脂壳的相变储能微胶囊浆料，将浆料用适量的去离子水稀释，静置陈化48小时后，再用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5~8小时，即得粒径为14～30μm（平均粒径为26μm）有机硅氮烷聚合物树脂为壳材的相变储能微胶囊粉末。
实施例2有机硅氮烷聚合物树脂为壳材的相变储能微胶囊的制备
（1）水相的配制
称取6克十二烷基苯磺酸钠于烧杯中，加去离子水至100克，搅拌，使乳化剂完全溶解，，配制成6%的乳化剂水溶液，得到水相；
（2）油相的配制
在烧杯中加入15克有机硅氮烷聚合物和40克乙酸乙酯混合，搅拌至完全互溶后，加入60克正十八烷，在20～30℃条件下完全互溶，再添加0.03克辛酸亚锡，搅拌混匀，制得油相；
（3）乳液的形成
将水相在70℃下保温10分钟后，将油相加入到水相中，5000rpm高速分散15分钟，形成稳定的水包油型乳液；
（4）微胶囊的形成
乳化结束，降低转速，向上述乳液加入0.05克的辛酸亚锡，在70℃下保温30分钟后，升温至85℃，继续反应6小时结束反应，得到具有超薄的有机硅氮烷聚合物树脂壳的相变储能微胶囊浆料，将浆料用适量的去离子水稀释，静置陈化48小时后，再用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5~8小时，即得粒径为900nm～2.4μm（平均粒径为1.5μm）有机硅氮烷聚合物树脂为壳材的相变储能微胶囊粉末。
实施例3有机硅氮烷聚合物树脂为壳材的相变储能微胶囊的制备
（1）水相的配制
称取60克10%苯乙烯马来酸酐共聚物钠盐(SMA-Na)水溶液于烧杯中，加去离子水至100克，搅拌，使乳化剂完全溶解，用冰醋酸调节pH：4.0～5.0，配制成5%的乳化剂水溶液，得到水相；
（2）油相的配制
在烧杯中加入20克有机硅氮烷聚合物和40克乙酸乙酯混合，搅拌至完全互溶后，加入60克正十六烷，在20～30℃条件下完全互溶，再添加0.035克铂（0）-二乙烯基四甲基二硅氧烷复合物，搅拌混匀，制得油相；
（3）乳液的形成
将水相在70℃下保温10分钟后，将油相加入到水相中，1000rpm高速分散15分钟，形成稳定的水包油型乳液；
（4）微胶囊的形成
乳化结束，降低转速，向上述乳液加入0.08克的铂（0）-二乙烯基四甲基二硅氧烷复合物，在70℃下保温30分钟后，升温至95℃，继续反应6小时结束反应，得到具有超薄的有机硅氮烷聚合物树脂壳的相变储能微胶囊浆料，将浆料用适量的去离子水稀释，静置陈化48小时后，再用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5~8小时，即得240nm～560nm（平均粒径为510nm）有机硅氮烷聚合物树脂为壳材的相变储能微胶囊粉末。
实施例4有机硅氮烷聚合物树脂为壳材的相变储能微胶囊的制备
（1）水相的配制
称取4克十二烷基硫酸钠于烧杯中，加去离子水至100克，搅拌，使乳化剂完全溶解，配制成4%的乳化剂水溶液，得到水相；
（2）油相的配制
在烧杯中加入18克有机硅氮烷聚合物和40克乙酸乙酯混合，搅拌至完全互溶后，加入60克正二十烷，在20～30℃条件下完全互溶，再添加0.035克二月桂酸二丁基锡，搅拌混匀，制得油相；
（3）乳液的形成
将水相在70℃下保温10分钟后，将油相加入到水相中，8000rpm高速分散15分钟，形成稳定的水包油型乳液；
（4）微胶囊的形成
乳化结束，降低转速，向上述乳液加入0.075克二月桂酸二丁基锡，在70℃下保温30分钟后，升温至90℃，继续反应6小时结束反应，得到具有超薄的有机硅氮烷聚合物树脂壳的相变储能微胶囊浆料，将浆料用适量的去离子水稀释，静置陈化48小时后，再用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5~8小时，即得570nm～860nm（平均粒径为774nm）有机硅氮烷聚合物树脂为壳材的相变储能微胶囊粉末。
实施例5有机硅氮烷聚合物树脂为壳材的相变储能微胶囊的制备
（1）水相的配制
称取60克10%苯乙烯马来酸酐共聚物钠盐(SMA-Na)水溶液于烧杯中，加去离子水至100克，搅拌，使乳化剂完全溶解，用冰醋酸调节pH：4.0～5.0，配制成5%的乳化剂水溶液，得到水相；
（2）油相的配制
在烧杯中加入14克有机硅氮烷聚合物和40克乙酸乙酯混合，搅拌至完全互溶后，加入60克正二十二烷，在20～30℃条件下完全互溶，再添加0.03克铂（0）-二乙烯基四甲基二硅氧烷复合物，搅拌混匀，制得油相；
（3）乳液的形成
将水相在70℃下保温10分钟后，将油相加入到水相中，5500rpm高速分散15分钟，形成稳定的水包油型乳液；
（4）微胶囊的形成
乳化结束，降低转速，向上述乳液加入0.06克的铂（0）-二乙烯基四甲基二硅氧烷复合物，在70℃下保温30分钟后，升温至85℃，继续反应6小时结束反应，得到具有超薄的有机硅氮烷聚合物树脂壳的相变储能微胶囊浆料，将浆料用适量的去离子水稀释，静置陈化48小时后，再用去离子水洗涤，减压过滤，得到滤饼，置于70℃烘箱中干燥5~8小时，即得粒径为480nm～2.0μm（平均粒径为1.1μm）有机硅氮烷聚合物树脂为壳材的相变储能微胶囊粉末。
效果例1
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44.56℃，熔化吸热焓为200.0J/g，结晶放热焓为194.9J/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1在237.73℃以下微胶囊具有良好的稳定性。
效果例2 微胶囊机械强度测试
利用超声波振荡器产生高频机械振荡，在介质中形成超声波，以正压和负压高频交替变化在介质中疏密相间地向前辐射传播，使介质中不断产生无数小气泡并不断破裂，即所谓的“空化效应”，从而产生一连串的爆炸释放出巨大能量，对周围形成巨大冲击，对微胶囊壳材表面不断进行冲击，造成机械强度较弱的微胶囊破裂。在超声振荡下，每隔一段时间，取样进行扫描电镜观察微胶囊样品破损情况，来达到测试微胶囊机械强度的目的。
将同等质量的两种微胶囊粉末分散到同等质量的去离子水中，分别装入两个规格一样的锥形瓶中，置于超声波振荡器中，超声振荡，每隔15分钟取样观察微胶囊破损情况。
测试结果：（1）图8为市售的界面聚合法制备的聚脲树脂为壳材的相变微胶囊样品，在超声振荡15分钟后，取样的扫描电镜图，观察到有50%以上出现微胶囊破裂。
（2）图9为本申请专利的界面聚合法制备的有机硅氮烷聚合物树脂为壳材的相变微胶囊样品（本发明实施例5）在超声振荡30分钟后，取样的扫描电镜图，观察到几乎无微胶囊破裂。
效果例3 微胶囊的密封性能测试
利用微胶囊的聚脲树脂壳材和有机硅氮烷聚合物树脂壳材，都不溶于无水乙醇，而微胶囊的芯材正二十二烷，溶于乙醇，不溶于水的特性，可将一定量的微胶囊样品浸泡于无水乙醇中，机械搅拌15分钟，后加入两倍乙醇的水，继续搅拌15分钟后，静置分层，收集上层微胶囊浆料平铺于吸油纸上，置于烘箱70℃干燥2小时后取出样品，用洗耳球吹掉吸油纸的微胶囊粉末，观察吸油纸面沾有油渍情况。通过无水乙醇将带有裂纹及细孔壳的微胶囊的芯材正二十二烷溶出来，加入水后，使得比重较轻的微胶囊和溶出来的芯材正二十二烷浮于醇水溶液上层，溶出来的芯材正二十二烷于70℃会熔化成油，粘在吸油纸上形成油渍，从而达到检测微胶囊的密封性能。
（1）将一定量的市售的界面聚合法制备的聚脲树脂为壳材，正二十二烷为芯材的相变微胶囊样品，按照上述微胶囊的密封性能测试方法进行测试，观察到吸油纸面有油渍现象。将超声振荡15分钟后的此微胶囊样品，按照上述微胶囊的密封性能测试方法进行测试，观察到整张吸油纸面上星罗密布般地沾满油渍。说明市售的界面聚合法制备的聚脲树脂为壳材，正二十二烷为芯材的相变微胶囊样品的密封性很差，有些微胶囊壳材存在裂纹或细孔等破损情况。
（2）将一定量的本专利的界面聚合法制备的有机硅氮烷聚合物树脂为壳材，正二十二烷为芯材的相变微胶囊样品（本发明实施例5），按照上述微胶囊的密封性能测试方法进行测试，观察到吸油纸面没有油渍现象。将超声振荡30分钟后的此微胶囊样品，按照上述微胶囊的密封性能测试方法进行测试，观察到吸油纸面上几乎没有油渍。说明本专利的界面聚合法制备的有机硅氮烷聚合物树脂为壳材，正二十二烷为芯材的相变微胶囊样品的密封性优良，微胶囊壳材几乎不存在裂纹或细孔等破损情况。

Claims (10)

  1. 一种机硅氮烷聚合物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）配制水相：配制乳化剂的水溶液，得到水相；
    2）配制油相：硅氮烷聚合物、有机溶剂、相变储能材料以及催化剂混合均匀得到油相；
    3）制备乳液：将水相和油相混合，并通过机械分散获得水包油型乳液；
    4）在使乳液升温至55～75℃，加入催化剂，升温至80～95℃恒温至获得有机硅氮烷聚合物树脂为壳材的相变储能微胶囊。
  2. 根据权利要求1所述的制备方法，所述的乳化剂选自水包油型乳化剂，优选乳化剂的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。
  3. 根据权利要求1所述的制备方法，所述的步骤1）中水相中乳化剂的浓度为1-10%，优选为2.5%-6.0%，更优选为5%。
  4. 根据权利要求1所述的制备方法，在本发明的技术方案中，所述的步骤2）中硅氮烷聚合物和相变储能材料的配比为1:2-1:5，优选为1:2.8-1:4.5。
  5. 根据权利要求1所述的制备方法，在本发明的技术方案中，相变储能材料选自正烷烃中的一种或几种，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。
  6. 根据权利要求1所述的制备方法，所述的步骤2）和3）中催化剂选自铂（0）-二乙烯基四甲基二硅氧烷复合物、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。
  7. 根据权利要求1所述的制备方法，所述的步骤2）中催化剂加入量为硅氮烷聚合物：催化剂=1:0.001-0.005，优选为1:0.001-0.003。
  8. 根据权利要求1所述的制备方法，所述的步骤3）中催化剂加入量为硅氮烷聚合物：催化剂=1:0.002-0.01，优选为1:0.002-0.006。
  9. 根据权利要求1-8任一项所述的制备方法制备得到的机硅氮烷聚合物树脂为壳材的相变储能微胶囊。
  10. 一种机硅氮烷聚合物树脂为壳材的相变储能微胶囊，其包括硅氮烷聚合物的外壳，以及相变储能材料的内核，所述相变储能材料为正烷烃；所述硅氮烷聚合物与相变储能材料的质量比为1:2-1:5；
    优选地，所述相变储能微胶囊的粒径为300nm-100μm。
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