WO2020042266A1 - 一种双重乳化玻璃毛细管微流控芯片及其制成的相变微胶囊 - Google Patents

一种双重乳化玻璃毛细管微流控芯片及其制成的相变微胶囊 Download PDF

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WO2020042266A1
WO2020042266A1 PCT/CN2018/107925 CN2018107925W WO2020042266A1 WO 2020042266 A1 WO2020042266 A1 WO 2020042266A1 CN 2018107925 W CN2018107925 W CN 2018107925W WO 2020042266 A1 WO2020042266 A1 WO 2020042266A1
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glass capillary
phase change
small
microfluidic chip
nosed
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French (fr)
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陈颖
李俊
贾莉斯
李亦昂
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Guangdong University of Technology
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Guangdong University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • 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
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
    • 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

Definitions

  • the invention belongs to the technical field of preparation of phase-change microcapsule materials, and particularly relates to a double-emulsion glass capillary microfluidic chip and a phase-change microcapsule made by the same.
  • phase change materials are a type of energy storage materials that can store and release a large amount of latent heat. They are widely used in heat storage and temperature control. However, because phase change materials are generally corrosive, have low heat exchange efficiency, and solid-liquid transformation, Limits the use of phase change materials.
  • Microencapsulated phase change material is a new technology for preparing phase change microcapsules by applying capsule technology to phase change materials. Phase change microcapsules usually consist of two parts: the core of the phase change material and the shell of the polymer material.
  • phase change microcapsules have advantages that pure phase change materials do not have, such as a larger specific surface area and a larger thermal conductivity, which isolates the core material from contact with the external environment, improves the stability of the phase change material, and prevents the core material from leaking easily. Due to these excellent characteristics, phase change microcapsules have been widely used in the fields of building energy saving, electronic heat dissipation, clothing textile, heat transfer medium, military, agriculture and other fields.
  • phase change microcapsules include physical and chemical methods and physical chemical methods, such as interfacial polymerization method, double emulsion method, gel sol method, suspension method, in-situ polymerization method, and the like. These traditional methods have the advantages of mature technology and large output. Some methods have been applied to the mass production of capsules in industry. However, most of these methods use mechanical methods such as mechanical stirring and spraying to emulsify phase change materials, resulting in capsules with the disadvantages of difficult to control particle size, large polydispersity, low coverage, and easy breakage. Insufficient control of the cystic nature and the capsule wall of the phase change microcapsules during the preparation process makes the use of phase change microcapsules limited.
  • microfluidic technology in the field of emulsion preparation has gradually matured.
  • microfluidic chips it has been possible to prepare monodispersed droplets such as monolayers, bilayers and even multilayers.
  • various materials can be synthesized and prepared in microfluidic chips.
  • the dual droplet preparation technology is a new technique for preparing stable dual droplets by controlling the interaction of the three-phase fluid.
  • the structure and size of the dual droplets can be changed by changing the flow rate of the three-phase fluid in the microchip. Precise control.
  • dual-droplet preparation technology combined with UV curing to prepare phase change microcapsules with controllable core and wall size.
  • the primary object of the present invention is to provide a double emulsified glass capillary microfluidic chip.
  • the shell thickness and core material size of the prepared phase change microcapsules were controlled.
  • Another object of the present invention is to provide a method for preparing phase change microcapsules by using the above double-emulsified glass capillary microfluidic chip.
  • Another object of the present invention is to provide a phase change microcapsule prepared by the above method.
  • a double emulsified glass capillary microfluidic chip comprising a large glass capillary, a small glass capillary, a large-nosed glass capillary, a small-nosed glass capillary, two conical centrifuge tubes, and a glass slide abutment;
  • the small-nosed glass capillary is coaxially inserted into the inside of the large-nosed glass capillary, and the two-nosed nozzles are located on the same side.
  • the distance is 10-500 microns; the large-nosed glass capillary is inserted in the direction of the pointed glass capillary from the entrance of the large glass capillary, the small glass capillary is inserted from the large glass capillary exit, and the pointed tip of the large-nosed glass capillary extends into the small glass capillary. 10-100 microns; large glass capillary placed on a glass slide abutment;
  • the two conical centrifuge tubes are inverted at the entrances of the large-tip glass capillary and the large-capillary glass capillary, respectively, and are used between the conical centrifuge tube, the large-tip glass capillary, the small-tip glass capillary and the slide base.
  • the sealant forms a first closed liquid storage tank, and the sealant forms a second closed liquid storage tank between the conical centrifuge tube, the large glass capillary tube, the large-nosed glass capillary tube, and the glass slide base;
  • the inlets of the small-nosed glass capillary and the two conical centrifuge tubes are connected to three syringe pumps through Teflon catheters, respectively.
  • the outer diameter of the large glass capillary is 500-1000 microns, and the inner diameter is 400-900 microns; the outer diameter of the small glass capillary and the large-nosed glass capillary is 300-800 microns, and the inner diameter is 200-700 microns; the small-tip glass
  • the outer diameter of the capillary is 100-600 microns and the inner diameter is 50-500 microns; the ratio of the internal diameter of the large-nosed glass capillary to the internal diameter of the nozzle is greater than 1 and less than 10; The ratio is greater than 1 and less than 10.
  • the sealant is epoxy resin.
  • a method for preparing a phase-change microcapsule by using the above double-emulsified glass capillary microfluidic chip includes the following steps:
  • Disperse phase 1 dispersed phase 2 and continuous phase are pushed into the Teflon catheter from the syringe pump and passed into the double emulsified glass capillary microfluidic chip. Among them, dispersed phase 1 is introduced into the microfluid from the small-tip glass capillary. Control chip, dispersed phase 2 is passed from the first closed liquid storage tank into the microfluidic chip, and continuous phase is passed from the second closed liquid storage tank into the microfluidic chip;
  • step (3) The capsules obtained in step (3) are filtered, repeatedly washed with deionized water and anhydrous ethanol, and dried at room temperature to obtain phase change microcapsules with controllable thickness and capsule core.
  • the dispersed phase 1 in step (1) is a phase change material;
  • the dispersed phase 2 is a photocuring agent monomer, a mixture of a surfactant 1 and a photoinitiator, and a mass fraction of the surfactant 1 is 0-3%.
  • the mass fraction of the initiator is 1-2%;
  • the continuous phase is a mixture of surfactant 2 and water, and the mass fraction of the surfactant 2 is 1-10%.
  • the phase change material is an alkane or an alkane halide;
  • the photocuring agent monomer is an unsaturated polyester resin;
  • the surfactant 1 is an oil-soluble ionic or non-ionic surfactant;
  • the photoinitiator is Darocur 1173;
  • the surfactant 2 is a water-soluble ionic or non-ionic surfactant.
  • phase change material is heptadecane
  • the photocuring agent monomer is 1,6-hexanediol diacrylate (HDDA)
  • the surfactant 1 is Span-80 (Span-80)
  • the The surfactant 2 is polyvinyl alcohol.
  • the syringe pump in step (1) separately controls the three-phase flow rate into the microfluidic chip, wherein the flow rate of the dispersed phase 1 is 2-30 ⁇ l / min, and the flow rate of the dispersed phase 2 is 5-50 ⁇ l / min.
  • the continuous phase The flow rate is 50-500 ⁇ l / min.
  • the wavelength of the ultraviolet light of the ultraviolet lamp light source in step (2) is 360 nm, and the radiation intensity of the end of the small glass capillary is greater than 100 mW / cm 2 .
  • phase change microcapsule prepared according to the above method.
  • the phase change microcapsule is composed of a polyester resin as a wall material and an alkane or alkane halide as a core material.
  • the core size of the phase change microcapsule is in the range of 30-500 ⁇ m. Internally controllable, its capsule wall thickness can be controlled within the range of 1-200 ⁇ m, the overall capsule size range is 30-600 ⁇ m, the phase change microcapsule particle size deviation is less than 4 ⁇ m, the phase change microcapsules with the target preparation size have a proportion greater than 70%, and the core The material content is 50-90%.
  • Multi-emulsion droplet microfluidics and UV curing technology are used to emulsify and encapsulate the phase change material in the microfluidic chip.
  • the double droplets generated by ultraviolet light irradiation make the capsule wall material solidify and finally encapsulate the capsule core to form a phase change microcapsule.
  • the present invention uses multiple emulsified droplet microfluidic chips to prepare phase-change material microemulsions, which greatly enhances the controllability of the prepared capsules and increases the practical value of the capsules.
  • the core material is precisely controlled using a high-precision syringe pump
  • the emulsification process of the wall material and the microfluidic chip yields a phase change material microemulsion with good monodispersity and high sphericity.
  • the use of ultraviolet light to cure the wall material reduces the preparation time and cost, and also improves the controllability of the wall material.
  • the present invention has the following advantages and beneficial effects:
  • the invention can simply and effectively control the core size and wall thickness of phase change microcapsules, so that the mechanical properties and energy storage performance of the prepared capsules can be effectively controlled, and phase change microcapsule materials suitable for various use requirements can be obtained. At the same time, the size of the phase change microcapsules can be controlled, and the particle size can be reduced.
  • the preparation process has the advantages of simple equipment, easy operation, high raw material utilization rate, easy control of product particle size, shell thickness and core material size, no noise, no harmful waste, low energy consumption, etc., suitable for scientific research and industrial production. Promotion and application of phase change microcapsules.
  • Figure 1 is a system for preparing phase change microcapsules using a double-emulsion glass capillary microfluidic chip, where 1 is a syringe pump; 2 is a Teflon catheter; 3 is a conical centrifuge tube; 4 is an ultraviolet light source; 5 is a large glass Capillaries; 6 is a small glass capillary; 7 is a glass slide abutment; 8 is a large-nosed glass capillary; 9 is a small-nosed glass capillary.
  • FIG. 1 The structure of the double-emulsion glass capillary microfluidic chip used in the following examples is shown in FIG. 1, which includes a large glass capillary 5, a small glass capillary 6, a large pointed glass capillary 8, a small pointed glass capillary 9, and two conical centrifuges. Tube 3 and slide abutment 7;
  • the small-nosed glass capillary 9 is coaxially inserted into the inside of the large-nosed glass capillary 8 and both of the pointed noses are located on the same side
  • the distance between the tips of the two is 10-500 microns;
  • the large-nosed glass capillary 8 is inserted in the direction of the nozzle from the entrance of the large glass capillary 5;
  • the small glass capillary 6 is inserted from the large-glass capillary 5 outlet;
  • the pointed mouth extends into the small glass capillary 6 to 10-100 microns;
  • the large glass capillary 5 is placed on a glass slide base;
  • the two conical centrifuge tubes 3 are inverted at the entrance of the large-tip glass capillary 8 and the large-capillary glass capillary 5, respectively; the conical centrifuge tube 3, the large-tip glass capillary 8, the small-tip glass capillary 9 and the glass carrier
  • a sealant is used to form a first closed liquid storage tank between the abutment 7 and a sealant is used to form a second seal between the conical centrifuge tube 3, the large glass capillary 5, the large-nosed glass capillary 8 and the glass slide abutment 7.
  • Liquid storage tank Liquid storage tank
  • the inlets of the small-nosed glass capillary 9 and the two conical centrifuge tubes 3 are connected to three injection pumps 1 through Teflon catheters 2 respectively.
  • the outer diameter of the large glass capillary is 500-1000 microns, and the inner diameter is 400-900 microns; the outer diameter of the small glass capillary and the large-nosed glass capillary is 300-800 microns, and the inner diameter is 200-700 microns; the small-tip glass
  • the outer diameter of the capillary is 100-600 microns and the inner diameter is 50-500 microns; the ratio of the internal diameter of the large-nosed glass capillary to the internal diameter of the nozzle is greater than 1 and less than 10, and the internal and internal diameters of the small-nosed glass capillary The ratio is greater than 1 and less than 10.
  • the sealant is epoxy resin.
  • a method for preparing a phase-change microcapsule by using the above double-emulsified glass capillary microfluidic chip includes the following steps:
  • step (3) The capsule obtained in step (3) is filtered, repeatedly washed three times with deionized water and absolute ethanol, and dried at room temperature to obtain a shell thickness of about 100 ⁇ m, a capsule core diameter of about 300 ⁇ m, and a total diameter of about 500 ⁇ m. Phase change microcapsules with a polydispersity coefficient of less than 3%.
  • the flow rate of the syringe pump was adjusted to 150 ⁇ l / min, 20 ⁇ l / min, and 10 ⁇ l / min, respectively.
  • the other steps were the same as in Example 1.
  • the thickness of the finally obtained capsule shell is about 50 ⁇ m, the diameter of the capsule core is about 240 ⁇ m, the total diameter of the capsule is about 340 ⁇ m, and the polydispersity coefficient is less than 3%.
  • the flow rate of the syringe pump was adjusted to 800 ⁇ l / min, 5 ⁇ l / min, and 5 ⁇ l / min, respectively.
  • the other steps were the same as in Example 1.
  • the thickness of the finally obtained capsule shell is about 10 ⁇ m, the diameter of the capsule core is about 20 ⁇ m, the total diameter of the capsule is about 60 ⁇ m, and the polydispersity coefficient is less than 3%.

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Abstract

一种双重乳化玻璃毛细管微流控芯片及其制成的相变微胶囊，使用多重乳化液滴微流控芯片制备相变材料微乳液，极大的增强了对所制备的胶囊的可控性，增加了胶囊的实用价值；使用高精度的注射泵（1）精确控制芯材和壁材在微流控芯片中的乳化过程，得到单分散性好，球形度高的相变材料微乳液。使用紫外光固化壁材，降低了制备时间和成本，也提高了壁材的可控性。制备过程具有设备简单，操作简易，原材料利用率高，易于控制产品粒径、球形度、壳层厚度和芯材大小，无噪音，无有害废弃物，能耗低等优点，适合于科研和工业生产各种相变微胶囊的推广应用。

Description

一种双重乳化玻璃毛细管微流控芯片及其制成的相变微胶囊 技术领域
本发明属于相变微胶囊材料的制备技术领域，具体涉及一种双重乳化玻璃毛细管微流控芯片及其制成的相变微胶囊。
背景技术
近年来，热能储存技术(TES)已经成为一项重要的节能新技术，在提高能源利用效率方面起到了十分显著的作用，成为能源科学领域中一个十分活跃的研究热点。相变材料是一类可以储存和释放出大量潜热的储能材料，被广泛应用于热量储存和温度控制方面，但是由于相变材料普遍具有腐蚀性、换热效率低以及固液转变等原因，限制了相变材料的使用。微胶囊化相变材料是一种将胶囊技术应用到相变材料中制备出相变微胶囊的新技术。通常相变微胶囊由两部分组成：相变材料核心和高分子材料外壳，高分子材料外壳将相变材料完全包覆在内部形成粒径为微米甚至纳米的胶囊结构。相变微胶囊具有纯相变材料所不具有的优点，例如更大的比表面积，更大的导热系数，隔绝芯材与外界环境的接触提高相变材料的稳定性，芯材不易泄漏。由于这些优异的特性，使得相变微胶囊目前已经广泛应用于建筑节能，电子散热，衣物纺织，传热工质，军事，农业等领域中。
目前常用的制备相变微胶囊的方法包括物理法和化学法以及物理化学法，如界面聚合法，复乳法，凝胶溶胶法，悬浮法，原位聚合法等。这些传统方法具有工艺成熟，产量大的优点，有些方法已经应用于工业上胶囊的大批量生产。但是，这些方法大多数使用的是机械搅拌和喷雾 等机械方法对相变材料进行乳化，导致制备出的胶囊具有粒径难以控制，多分散性较大，包覆率低，易破损等缺点。制备过程中对于决定相变微胶囊使用性能的囊性和囊壁的控制不足，使得相变微胶囊的使用受到限制。
近年来微流控技术在乳液制备领域的发展逐渐成熟，使用微流控芯片已经可以制备出如单层、双层甚至多层的单分散液滴。通过集成其它化学物理方法，可以在微流控芯片中进行各种材料的合成制备。双重液滴制备技术是一种通过控制三相流体的相互作用力来制备出稳定的双重液滴的新技术，通过改变三相流体在微芯片中的流速可以对双重液滴的结构和尺寸进行精确控制，目前使用双重液滴制备技术结合紫外光固化制备囊芯和囊壁尺寸可控的相变微胶囊还鲜有报道。
发明内容
为了克服现有技术中存在的粒径不可控，粒径分布大，囊芯和囊壁不可控的不足，本发明的首要目的在于提供一种双重乳化玻璃毛细管微流控芯片，使用该芯片可以控制制备出来的相变微胶囊的壳层厚度和芯材大小。
本发明的又一目的在于提供一种利用上述双重乳化玻璃毛细管微流控芯片制备相变微胶囊的方法。
本发明的再一目的在于提供一种上述方法制备而成的相变微胶囊。
本发明目的通过以下技术方案实现：
一种双重乳化玻璃毛细管微流控芯片，包括大玻璃毛细管、小玻璃毛细管、大尖嘴玻璃毛细管、小尖嘴玻璃毛细管、2个锥形离心管和载玻片基台；
所述大尖嘴玻璃毛细管和小尖嘴玻璃毛细管只有出口端为尖嘴，小尖嘴玻璃毛细管的尖嘴同轴插入大尖嘴玻璃毛细管内部，并且两者尖嘴位于同一侧，两者尖端的距离为10-500微米；大尖嘴玻璃毛细管以尖嘴 方向从大玻璃毛细管的入口插入，小玻璃毛细管从大玻璃毛细管的出口插入，大尖嘴玻璃毛细管的尖嘴伸入小玻璃毛细管内10-100微米；大玻璃毛细管置于载玻片基台上；
所述2个锥形离心管分别倒扣于大尖嘴玻璃毛细管和大玻璃毛细管的入口处，锥形离心管、大尖嘴玻璃毛细管、小尖嘴玻璃毛细管和载玻片基台之间用密封胶形成第一封闭蓄液槽，锥形离心管、大玻璃毛细管、大尖嘴玻璃毛细管和载玻片基台之间用密封胶形成第二封闭蓄液槽；
所述小尖嘴玻璃毛细管和2个锥形离心管的入口分别通过特氟龙导管连接三个注射泵。
所述大玻璃毛细管的外径为500-1000微米，内径为400-900微米；小玻璃毛细管和大尖嘴玻璃毛细管的外径为300-800微米，内径为200-700微米；小尖嘴玻璃毛细管的外径为100-600微米，内径为50-500微米；所述大尖嘴玻璃毛细管的本身内径与尖嘴内径比大于1且小于10，小尖嘴玻璃毛细管的本身内径与尖嘴内径比大于1且小于10。
所述密封胶为环氧树脂胶。
一种利用上述的双重乳化玻璃毛细管微流控芯片制备相变微胶囊的方法，包括以下步骤：
(1)将分散相1、分散相2和连续相分别从注射泵推入特氟龙导管，通入双重乳化玻璃毛细管微流控芯片中，其中分散相1是从小尖嘴玻璃毛细管通入微流控芯片，分散相2是从第一封闭蓄液槽通入微流控芯片，连续相是从第二封闭蓄液槽通入微流控芯片；
(2)使用紫外灯光源在微流控芯片的小玻璃毛细管的末端进行照射，并在小玻璃毛细管的出口处收集固化后的胶囊；
(3)将步骤(3)中得到的胶囊进行过滤，使用去离子水和无水乙醇反复清洗，常温干燥，得到厚度和囊芯可控的相变微胶囊。
步骤(1)所述的分散相1为相变材料；所述分散相2为光固化剂单 体，表面活性剂1和光引发剂的混合物，表面活性剂1质量分数为0-3％，光引发剂质量分数为1-2％；所述连续相为表面活性剂2和水混合物，表面活性剂2质量分数为1-10％。
所述相变材料为烷烃类或烷烃卤代物；光固化剂单体为不饱和聚酯树脂；所述表面活性剂1为油溶性离子型或非离子型表面活性剂；所述光引发剂为德牢固1173(Darocur 1173)；所述表面活性剂2为水溶性离子型或非离子型表面活性剂。
所述相变材料为十七烷；所述光固化剂单体为1,6-己二醇双丙烯酸酯(HDDA)；所述表面活性剂1为司盘80(Span-80)；所述表面活性剂2为聚乙烯醇。
步骤(1)所述的注射泵分别控制三相的流入微流控芯片中的流速，其中分散相1的流速为2-30μl/min，分散相2的流速为5-50μl/min，连续相的流速为50-500μl/min。
步骤(2)所述的紫外灯光源的紫外光波长为360nm，对小玻璃毛细管的末端的辐照强度大于100mW/cm 2。
一种根据上述的方法制备得到的相变微胶囊，所述的相变微胶囊是由聚酯树脂作为壁材，烷烃类或烷烃卤代物作为芯材构成，其囊芯尺寸在30-500μm范围内可控，其囊壁厚度在1-200μm范围内可控，胶囊整体尺寸范围为30-600μm，相变微胶囊粒径偏差小于4μm，目标制备尺寸的相变微胶囊比重大于70％，芯材质量含量为50-90％。
本发明的原理是：
采用多重乳化液滴微流控和紫外光固化技术，在微流控芯片中进行相变材料的乳化和胶囊化过程。通过调节微流控芯片中三相流速比控制胶囊大小，囊芯大小和囊壁厚度，通过紫外光照射生成的双重液滴使得囊壁材料固化最终包裹囊芯形成相变微胶囊。本发明使用多重乳化液滴微流控芯片制备相变材料微乳液，极大的增强了对所制备的胶囊的可控 性，增加了胶囊的实用价值；使用高精度的注射泵精确控制芯材和壁材在微流控芯片中的乳化过程，得到单分散性好，球形度高的相变材料微乳液。使用紫外光固化壁材，降低了制备时间和成本，也提高了壁材的可控性。
与现有技术相比，本发明具有以下优点及有益效果：
本发明可以简便有效的控制相变微胶囊的囊芯大小和囊壁厚度，使得制备出的胶囊的机械性能和储能性能可以得到有效控制，得到适合各种使用需求的相变微胶囊材料，同时实现相变微胶囊的大小可控，粒径的低分散度等。制备过程具有设备简单，操作简易，原材料利用率高，易于控制产品粒径、壳层厚度和芯材大小，无噪音，无有害废弃物，能耗低等优点，适合于科研和工业生产各种相变微胶囊的推广应用。
附图说明
图1是利用双重乳化玻璃毛细管微流控芯片制备相变微胶囊的系统，其中1为注射泵；2为特氟龙导管；3为锥形离心管；4为紫外灯光源；5为大玻璃毛细管；6为小玻璃毛细管；7为载玻片基台；8为大尖嘴玻璃毛细管；9为小尖嘴玻璃毛细管。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
以下实施例使用的双重乳化玻璃毛细管微流控芯片结构如图1所示，包括大玻璃毛细管5、小玻璃毛细管6、大尖嘴玻璃毛细管8、小尖嘴玻璃毛细管9、2个锥形离心管3和载玻片基台7；
所述大尖嘴玻璃毛细管8和小尖嘴玻璃毛细管9只有出口端为尖嘴，小尖嘴玻璃毛细管9的尖嘴同轴插入大尖嘴玻璃毛细管8内部，并且两者尖嘴位于同一侧，两者尖端的距离为10-500微米；大尖嘴玻璃毛细管 8以尖嘴方向从大玻璃毛细管5的入口插入，小玻璃毛细管6从大玻璃毛细管5的出口插入，大尖嘴玻璃毛细管8的尖嘴伸入小玻璃毛细管6内10-100微米；大玻璃毛细管5置于载玻片基台上；
所述2个锥形离心管3分别倒扣于大尖嘴玻璃毛细管8和大玻璃毛细管5的入口处，锥形离心管3、大尖嘴玻璃毛细管8、小尖嘴玻璃毛细管9和载玻片基台7之间用密封胶形成第一封闭蓄液槽，锥形离心管3、大玻璃毛细管5、大尖嘴玻璃毛细管8和载玻片基台7之间用密封胶形成第二封闭蓄液槽；
所述小尖嘴玻璃毛细管9和2个锥形离心管3的入口分别通过特氟龙导管2连接三个注射泵1。
所述大玻璃毛细管的外径为500-1000微米，内径为400-900微米；小玻璃毛细管和大尖嘴玻璃毛细管的外径为300-800微米，内径为200-700微米；小尖嘴玻璃毛细管的外径为100-600微米，内径为50-500微米；所述大尖嘴玻璃毛细管的本身内径与尖嘴内径比大于1且小于10，小尖嘴玻璃毛细管的本身内径与尖嘴内径比大于1且小于10。
所述密封胶为环氧树脂胶。
实施例1：
一种利用上述的双重乳化玻璃毛细管微流控芯片制备相变微胶囊的方法，包括以下步骤：
(1)用10ml注射器取9ml十七烷作为分散相1，用10ml注射器取9ml含有2％质量分数司盘80和2％质量分数光固化剂的HDDA作为分散相2，用20ml注射器取15ml的2％质量分数的聚乙烯醇水溶液作为连续相；将分散相1、分散相2和连续相分别从注射泵推入特氟龙导管，通入双重乳化玻璃毛细管微流控芯片中，其中分散相1是从小尖嘴玻璃毛细管通入微流控芯片，分散相2是从第一封闭蓄液槽通入微流控芯片， 连续相是从第二封闭蓄液槽通入微流控芯片；调节注射泵的流速依次分别为150μl/min、50μl/min和10μl/min；
(2)使用紫外灯光源在微流控芯片的小玻璃毛细管的末端进行照射，并在小玻璃毛细管的出口处收集固化后的胶囊；(紫外灯光源的紫外光波长为360nm，对小玻璃毛细管的末端的辐照强度大于100mW/cm 2)
(3)将步骤(3)中得到的胶囊进行过滤，使用去离子水和无水乙醇反复清洗3次，常温干燥，得到外壳厚度约为100μm，囊芯直径约为300μm，总直径约为500μm，多分散系数小于3％的相变微胶囊。
实施例2：
调节注射泵的流速依次分别为150μl/min、20μl/min和10μl/min，其他步骤同实施例1。最后所得的胶囊外壳厚度约为50μm，囊芯直径约为240μm，胶囊总直径约为340μm，多分散系数小于3％。
实施例3
调节注射泵的流速依次分别为800μl/min、5μl/min和5μl/min，其他步骤同实施例1。最后所得的胶囊外壳厚度约为10μm，囊芯直径约为20μm，胶囊总直径约为60μm，多分散系数小于3％。
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。

Claims (10)

  1. 一种双重乳化玻璃毛细管微流控芯片，其特征在于：包括大玻璃毛细管、小玻璃毛细管、大尖嘴玻璃毛细管、小尖嘴玻璃毛细管、2个锥形离心管和载玻片基台；
    所述大尖嘴玻璃毛细管和小尖嘴玻璃毛细管只有出口端为尖嘴，小尖嘴玻璃毛细管的尖嘴同轴插入大尖嘴玻璃毛细管内部，并且两者尖嘴位于同一侧，两者尖端的距离为10-500微米；大尖嘴玻璃毛细管以尖嘴方向从大玻璃毛细管的入口插入，小玻璃毛细管从大玻璃毛细管的出口插入，大尖嘴玻璃毛细管的尖嘴伸入小玻璃毛细管内10-100微米；大玻璃毛细管置于载玻片基台上；
    所述2个锥形离心管分别倒扣于大尖嘴玻璃毛细管和大玻璃毛细管的入口处，锥形离心管、大尖嘴玻璃毛细管、小尖嘴玻璃毛细管和载玻片基台之间用密封胶形成第一封闭蓄液槽，锥形离心管、大玻璃毛细管、大尖嘴玻璃毛细管和载玻片基台之间用密封胶形成第二封闭蓄液槽；
    所述小尖嘴玻璃毛细管和2个锥形离心管的入口分别通过特氟龙导管连接三个注射泵。
  2. 根据权利要求1所述的一种双重乳化玻璃毛细管微流控芯片，其特征在于：所述大玻璃毛细管的外径为500-1000微米，内径为400-900微米；小玻璃毛细管和大尖嘴玻璃毛细管的外径为300-800微米，内径为200-700微米；小尖嘴玻璃毛细管的外径为100-600微米，内径为50-500微米；所述大尖嘴玻璃毛细管的本身内径与尖嘴内径比大于1且小于10，小尖嘴玻璃毛细管的本身内径与尖嘴内径比大于1且小于10。
  3. 根据权利要求1所述的一种双重乳化玻璃毛细管微流控芯片，其特征在于：所述密封胶为环氧树脂胶。
  4. 一种利用权利要求1所述的双重乳化玻璃毛细管微流控芯片制备 相变微胶囊的方法，其特征在于包括以下步骤：
    (1)将分散相1、分散相2和连续相分别从注射泵推入特氟龙导管，通入双重乳化玻璃毛细管微流控芯片中，其中分散相1是从小尖嘴玻璃毛细管通入微流控芯片，分散相2是从第一封闭蓄液槽通入微流控芯片，连续相是从第二封闭蓄液槽通入微流控芯片；
    (2)使用紫外灯光源在微流控芯片的小玻璃毛细管的末端进行照射，并在小玻璃毛细管的出口处收集固化后的胶囊；
    (3)将步骤(2)中得到的胶囊进行过滤，使用去离子水和无水乙醇反复清洗，常温干燥，得到厚度和囊芯可控的相变微胶囊。
  5. 根据权利要求4所述的方法，其特征在于：步骤(1)所述的分散相1为相变材料；所述分散相2为光固化剂单体，表面活性剂1和光引发剂的混合物，表面活性剂1质量分数为0-3％，光引发剂质量分数为1-2％；所述连续相为表面活性剂2和水混合物，表面活性剂2质量分数为1-10％。
  6. 根据权利要求5所述的方法，其特征在于：所述相变材料为烷烃类或烷烃卤代物；光固化剂单体为不饱和聚酯树脂；所述表面活性剂1为油溶性离子型或非离子型表面活性剂；所述光引发剂为德牢固1173；所述表面活性剂2为水溶性离子型或非离子型表面活性剂。
  7. 根据权利要求5所述的方法，其特征在于：所述相变材料为十七烷；所述光固化剂单体为1,6-己二醇双丙烯酸酯；所述表面活性剂1为司盘80；所述表面活性剂2为聚乙烯醇。
  8. 根据权利要求4所述的方法，其特征在于：步骤(1)所述的注射泵分别控制三相的流入微流控芯片中的流速，其中分散相1的流速为2-30μl/min，分散相2的流速为5-50μl/min，连续相的流速为50-500μl/min。
  9. 根据权利要求4所述的方法，其特征在于：步骤(2)所述的紫 外灯光源的紫外光波长为360nm，对小玻璃毛细管的末端的辐照强度大于100mW/cm 2。
  10. 一种根据权利要求4-9任一项所述的方法制备得到的相变微胶囊，其特征在于：所述的相变微胶囊是由聚酯树脂作为壁材，烷烃类或烷烃卤代物作为芯材构成，其囊芯尺寸在30-500μm范围内可控，其囊壁厚度在1-200μm范围内可控，胶囊整体尺寸范围为30-600μm，相变微胶囊粒径偏差小于4μm，目标制备尺寸的相变微胶囊比重大于70％，芯材质量含量为50-90％。
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