WO2016029527A1 - Method for preparing paraffin microcapsule phase-change material modified by graphene oxide - Google Patents

Method for preparing paraffin microcapsule phase-change material modified by graphene oxide Download PDF

Info

Publication number
WO2016029527A1
WO2016029527A1 PCT/CN2014/087800 CN2014087800W WO2016029527A1 WO 2016029527 A1 WO2016029527 A1 WO 2016029527A1 CN 2014087800 W CN2014087800 W CN 2014087800W WO 2016029527 A1 WO2016029527 A1 WO 2016029527A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene oxide
paraffin
graphite
change material
phase change
Prior art date
Application number
PCT/CN2014/087800
Other languages
French (fr)
Chinese (zh)
Inventor
陆洪彬
张秋香
陈建华
唐伟
王金鑫
陆玉
Original Assignee
海安南京大学高新技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 海安南京大学高新技术研究院 filed Critical 海安南京大学高新技术研究院
Publication of WO2016029527A1 publication Critical patent/WO2016029527A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • 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 field of functional polymer materials, and particularly relates to a preparation method of a graphene oxide modified paraffin microcapsule phase change material.
  • Phase-state energy storage-discharge materials have the characteristics of automatic heat absorption and release, which can effectively control the temperature within a specific temperature range.
  • PCMs Phase-state energy storage-discharge materials
  • MicroPCMs use microcapsule technology to coat phase change materials to form microparticle composite phase change materials with sizes ranging from 1 ⁇ m to 1000 ⁇ m.
  • MicroPCMs can effectively solve the problem of PCMs leakage, prevent the reaction of phase change materials with the surrounding environment, improve the use efficiency of phase change materials, and increase the heat transfer surface area, which is a high application value material.
  • the commonly used microcapsule wrapping materials often use melamine-formaldehyde resin and urea-formaldehyde resin.
  • These coated wall materials have problems such as insufficient toughness and easy cracking; and a small amount of research uses acrylate to improve material properties, although the wall material performance is improved.
  • the wall material has low enveloping rate of the core material and poor thermal conductivity, resulting in high production cost and reduced practicability.
  • Graphene is a hotspot in current material science research.
  • the invention provides a method for preparing a graphene oxide modified paraffin microcapsule phase change material according to the shortcomings of the present microcapsules, and improves the thermal conductivity of the wrapping material by using the high specific surface area and high thermal conductivity of the graphene oxide;
  • the material is copolymerized with a negatively charged monomer, and the core material is emulsified with a cationic emulsifier, thereby providing a package power and improving the efficiency of encapsulation efficiency; and an O/W type high dispersion and high stability phase change paraffin emulsion is prepared by inverse emulsification method, and then A microcapsule phase change material having a core-shell structure is formed by a core-shell type in-situ polymerization principle.
  • the paraffin microcapsules prepared by the method have greatly improved the thermal conductivity and the wall material, increased the core/shell ratio, increased the enthalpy of the phase change material, and the yield was also obtained. Greatly improved, reaching more than 70%, with good practical economic value.
  • the present invention adopts the following technical solution: a method for preparing a graphene oxide modified paraffin microcapsule phase change material, comprising the following steps:
  • the remaining potassium permanganate is added in two portions to maintain stirring;
  • the high temperature water bath is at a temperature of 80-90 ° C. , stirring speed is 300-500 rpm, reaction time is 4h, complete deep oxidation of graphite;
  • adding deionized water wherein the mass ratio of graphite to deionized water is 1: (60-80)
  • after hydrolysis reaction adding 30Vol% Neutralizing unreacted potassium permanganate with hydrogen peroxide, ending with a bright yellow color of the solution, and then adding a 10 Vol% hydrochloric acid solution, the mass ratio of 30 Vol% hydrogen peroxide to 10 Vol% hydrochloric acid is 1: (1.5-2), Vacuum filtration, Washed with deionized water to pH 7, dried and ground at 60 ° C to obtain graphene oxide.
  • the prepared graphene oxide was added to deionized water and ultrasonically dispersed for about 1 h to obtain 1-5% graphene oxide solution. use;
  • paraffin emulsion Add paraffin, nonionic emulsifier and ionic emulsifier to the stirred tank, raise the temperature to 65-75 ° C, add the graphite dispersed in deionized water, stir at 500-1000 r / min Stirring at a speed of 0.5-1 h to obtain an O/W paraffin emulsion;
  • Post-treatment vacuum filtration, petroleum ether washing, water washing, vacuum drying at 40-50 ° C, and pulverization by a jet mill to obtain paraffin microcapsule powder.
  • the graphite described in the formulation has a natural flake graphite particle size of 32-200 mesh.
  • the strong acid described in the formulation is 98% concentrated sulfuric acid, and the strong oxidizing agent is sodium nitrate or potassium permanganate.
  • the mass ratio of graphite, concentrated sulfuric acid, sodium nitrate and potassium permanganate is 1: (25-75): (0.5-1): (6-18).
  • paraffin wax described in the formulation is at least one of German RUBITHERM phase change paraffin wax (phase transition point 34 ° C, 44 ° C and 54 ° C).
  • the nonionic emulsifier comprises one or more of Tween-80, Tween-60, Span-80, Span-60, OP-10; the cationic emulsifier comprises hexadecane At least one of trimethylammonium bromide, dodecyl ammonium chloride, and cetylpyridinium bromide.
  • the mass ratio of the paraffin wax, the nonionic emulsifier, the cationic emulsifier and the deionized water in the paraffin emulsion is 1:0.08:0.04:12
  • the water-soluble initiator includes at least one of ammonium persulfate, potassium persulfate, and a water-soluble azo initiator.
  • the monomer is methyl (meth)acrylate, ethyl methacrylate, butyl acrylate, isooctyl acrylate, lauryl methacrylate, n-octyl methacrylate, (meth)acrylic acid. And at least one of hydroxyethyl acrylate.
  • the mass ratio of the paraffin wax, the monomer, and the water-soluble initiator is 1:1:0.02.
  • the microcapsule material prepared by the invention overcomes various shortcomings such as poor wall strength, low heat conduction efficiency, low package efficiency and low latent heat of phase change existing in the microcapsule product, and has various kinds of surface through graphene oxide.
  • the reaction of the oxygen-containing group with the polymer improves the thermal stability and thermal conductivity of the paraffin microcapsule phase change material, prolongs the service life, and has a simple preparation process and environmental protection, and the obtained phase change material particle of the paraffin phase change microcapsule Uniform diameter, latent heat of phase change up to 160J/g, with significant performance advantages and good market prospects in the fields of building energy conservation, insulation products and floor heating.
  • 1 is an SEM image of a graphene oxide modified paraffin microcapsule phase change material.
  • the prepared graphene oxide is added to the deionized water while stirring In the middle, the ultrasonic dispersion is about 1 h, and a 2% graphene oxide solution is obtained for use.
  • Add 44 ° C paraffin, Tween-60, Siben-60 and lauryl ammonium chloride to the stirred tank, raise the temperature to 75 ° C, slowly add the graphite dispersed in deionized water (44 ° C paraffin: spit Wen-60: Siben-60: lauryl ammonium chloride: graphite dispersion 1:0.05:0.03:0.04:12), stirred at 500r/min stirring speed for 0.5h to obtain O/W paraffin emulsion .
  • the prepared graphene oxide was added to deionized water while stirring, and ultrasonically dispersed for about 1 hour to obtain a 3% graphene oxide solution to be used.
  • the prepared graphene oxide was added to deionized water while stirring, and ultrasonically dispersed for about 1 hour to obtain a 3% graphene oxide solution to be used.
  • Add 54 ° C paraffin, Tween-60, Siben-60 and lauryl ammonium chloride to the stirred tank, raise the temperature to 75 ° C, slowly add the graphite dispersed in deionized water (44 ° C paraffin: spit Wen-60: Siben-60: lauryl ammonium chloride: graphite dispersion 1:0.05:0.03:0.04:12), stirred at 500r/min stirring speed for 0.5h to obtain O/W paraffin emulsion .

Abstract

Provided is a method for preparing a paraffin microcapsule phase-change material modified by graphene oxide. The technical solution comprises: adding a concentrated acid and a strong oxidant to a low-temperature ice-water bath to oxidize graphite; successively adding deionized water, hydrogen peroxide and hydrochloric acid, vacuum filtrating, drying and grinding to obtain graphene oxide, and then adding the graphene oxide into deionized water to prepare a graphene oxide solution; adding paraffin, a non-ionic emulsifier and an ionic emulsifier into a stirring kettle, increasing the temperature and adding graphite under stirring to obtain a paraffin emulsion; adding an initiator into the paraffin emulsion for dissolution and dropwise adding monomers, vacuum filtrating after the completion, washing with petroleum ether, water-washing, drying in vacuum and crushing to obtain the paraffin microcapsule powder. The preparation method has the following beneficial effects: by the reaction of various oxygen-containing groups on the surface of the graphite oxide and the polymer, the thermal stability and the thermal conductivity of the paraffin microcapsule phase-change material are improved, and the service life is prolonged; the preparation is easy and environmentally friendly. The paraffin microcapsule phase-change material can be used in the fields such as building energy saving, thermal insulation products and floor heating, etc.

Description

一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法Method for preparing graphene oxide modified paraffin microcapsule phase change material 技术领域Technical field
本发明属于功能高分子材料领域，特别涉及到一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法。The invention belongs to the field of functional polymer materials, and particularly relates to a preparation method of a graphene oxide modified paraffin microcapsule phase change material.
背景技术Background technique
相态储能-放能材料(PCMs)具有自动吸放热的特点，能够有效地将温度控制在特定的温度范围内，目前正逐渐应用在建筑节能领域、保温材料等领域。而微胶囊相变材料(MicroPCMs)就是利用微胶囊技术，把相变材料包覆而形成尺寸在1μm-1000μm的微粒复合相变材料。MicroPCMs能有效的解决PCMs泄露问题，防止了相变物质与周围环境的反应，提高了相变材料的使用效率，同时增大了传热表面积，是一种高应用价值的材料。目前常用的微胶囊的包裹材料常选用三聚氰胺-甲醛树脂、脲醛树脂，这些包裹壁材存在韧性不足、易开裂等问题；也有少量研究里用丙烯酸酯来改进材料性能，虽然壁材性能得到提升，但壁材对芯材包裹率低、自身导热性能差，造成生产成本高、实用性降低，这些缺点严重影响了相变材料的推广应用。Phase-state energy storage-discharge materials (PCMs) have the characteristics of automatic heat absorption and release, which can effectively control the temperature within a specific temperature range. Currently, they are gradually applied in the fields of building energy conservation and insulation materials. Microcapsule phase change materials (MicroPCMs) use microcapsule technology to coat phase change materials to form microparticle composite phase change materials with sizes ranging from 1 μm to 1000 μm. MicroPCMs can effectively solve the problem of PCMs leakage, prevent the reaction of phase change materials with the surrounding environment, improve the use efficiency of phase change materials, and increase the heat transfer surface area, which is a high application value material. At present, the commonly used microcapsule wrapping materials often use melamine-formaldehyde resin and urea-formaldehyde resin. These coated wall materials have problems such as insufficient toughness and easy cracking; and a small amount of research uses acrylate to improve material properties, although the wall material performance is improved. However, the wall material has low enveloping rate of the core material and poor thermal conductivity, resulting in high production cost and reduced practicability. These shortcomings have seriously affected the popularization and application of phase change materials.
石墨烯作为目前材料科学研究的热点，石墨烯兼有石墨和碳纳米管的优良特点，如突出的导热、导电性能、力学强度等；而氧化石墨烯由于其表面接枝多种含氧基团(C＝O，C-OOH，C-OH等)，这些基团可以与聚合物工具形成纳米级“石墨-聚合物”复合材料，结合了两种材料的优点，形成高导热、高强度与高韧性的复合材料。 Graphene is a hotspot in current material science research. Graphene has excellent characteristics of graphite and carbon nanotubes, such as outstanding thermal conductivity, electrical conductivity, mechanical strength, etc.; and graphene oxide is grafted with various oxygen-containing groups due to its surface. (C=O, C-OOH, C-OH, etc.), these groups can form nanoscale "graphite-polymer" composites with polymer tools, combining the advantages of both materials to form high thermal conductivity, high strength and High toughness composite.
发明内容Summary of the invention
本发明针对目前微胶囊存在的诸多缺点，提供一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，利用氧化石墨烯的高比表面积及高导热率提高包裹材料的导热系数；利用壳材共聚负电性单体，芯材以阳离子乳化剂乳化，从而提供了提供包裹动力，提高效率包裹效率；采用反相乳化法制备出O/W型高分散、高稳定的相变石蜡乳液，然后通过核壳型原位聚合原理，形成核壳结构的微胶囊相变材料。相比于传统石蜡微胶囊，本方法制备的石蜡微胶囊，导热性及包裹壁材得到了很大提升，提高了核/壳比例，增大了相变材料的热焓，而且产率也得到很大提升，达到了70％以上，具有良好的实用经济价值。The invention provides a method for preparing a graphene oxide modified paraffin microcapsule phase change material according to the shortcomings of the present microcapsules, and improves the thermal conductivity of the wrapping material by using the high specific surface area and high thermal conductivity of the graphene oxide; The material is copolymerized with a negatively charged monomer, and the core material is emulsified with a cationic emulsifier, thereby providing a package power and improving the efficiency of encapsulation efficiency; and an O/W type high dispersion and high stability phase change paraffin emulsion is prepared by inverse emulsification method, and then A microcapsule phase change material having a core-shell structure is formed by a core-shell type in-situ polymerization principle. Compared with the traditional paraffin microcapsules, the paraffin microcapsules prepared by the method have greatly improved the thermal conductivity and the wall material, increased the core/shell ratio, increased the enthalpy of the phase change material, and the yield was also obtained. Greatly improved, reaching more than 70%, with good practical economic value.
为了实现上述目的，本发明采用如下技术方案：一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，包括以下步骤：In order to achieve the above object, the present invention adopts the following technical solution: a method for preparing a graphene oxide modified paraffin microcapsule phase change material, comprising the following steps:
1、氧化石墨烯的制备：在磁力搅拌器上，低温冰水浴，所述低温冰水浴的温度在0-4℃，搅拌速度为300-500rpm，反应时间为1.5h，向其中加入石墨、浓酸及强氧化剂，对石墨进行初步氧化；中温水浴，所述中温水浴温度在35-40℃，搅拌速度为300-500rpm，反应时间为2h，再逐次缓慢加入高锰酸钾，所述高锰酸钾分三次加入，在低温初步氧化阶段加入1/3，在中温氧化阶段，分两次加入剩余的高锰酸钾，保持搅拌；高温水浴，所述高温水浴温度在80-90℃，搅拌速度为300-500rpm，反应时间为4h，完成对石墨的深度氧化；加入去离子水，其中石墨与去离子水的质量比为1:(60-80)，水解反应之后，加入30Vol％过氧化氢中和未反应的高锰酸钾，以溶液呈亮黄色为终点，然后加入10Vol％的盐酸溶液，30Vol％过氧化氢与10Vol％盐酸的质量比为1:(1.5-2)，真空抽滤， 用去离子水洗涤至pH值为7，经60℃干燥、研磨得到氧化石墨烯，将制备的氧化石墨烯加入到去离子水中，超声分散1h左右，得到1-5％的氧化石墨烯溶液待用；1. Preparation of graphene oxide: on a magnetic stirrer, a low temperature ice water bath, the temperature of the low temperature ice water bath is 0-4 ° C, the stirring speed is 300-500 rpm, the reaction time is 1.5 h, and graphite is added thereto. Acid and strong oxidant, preliminary oxidation of graphite; medium temperature water bath, the temperature of the intermediate temperature water bath is 35-40 ° C, the stirring speed is 300-500 rpm, the reaction time is 2 h, and potassium permanganate is slowly added successively, Potassium permanganate is added in three portions, and 1/3 is added in the preliminary oxidation stage of low temperature. In the middle temperature oxidation stage, the remaining potassium permanganate is added in two portions to maintain stirring; the high temperature water bath is at a temperature of 80-90 ° C. , stirring speed is 300-500 rpm, reaction time is 4h, complete deep oxidation of graphite; adding deionized water, wherein the mass ratio of graphite to deionized water is 1: (60-80), after hydrolysis reaction, adding 30Vol% Neutralizing unreacted potassium permanganate with hydrogen peroxide, ending with a bright yellow color of the solution, and then adding a 10 Vol% hydrochloric acid solution, the mass ratio of 30 Vol% hydrogen peroxide to 10 Vol% hydrochloric acid is 1: (1.5-2), Vacuum filtration, Washed with deionized water to pH 7, dried and ground at 60 ° C to obtain graphene oxide. The prepared graphene oxide was added to deionized water and ultrasonically dispersed for about 1 h to obtain 1-5% graphene oxide solution. use;
2、石蜡乳液的制备：在搅拌釜中加入石蜡、非离子乳化剂和离子型乳化剂，升高温度至65-75℃，加入在去离子水中分散好的石墨，在500-1000r/min搅拌速度下搅拌0.5-1h，得到O/W型石蜡乳液；2. Preparation of paraffin emulsion: Add paraffin, nonionic emulsifier and ionic emulsifier to the stirred tank, raise the temperature to 65-75 ° C, add the graphite dispersed in deionized water, stir at 500-1000 r / min Stirring at a speed of 0.5-1 h to obtain an O/W paraffin emulsion;
3、石蜡微胶囊乳液的制备：在500-1000转/分钟的搅拌速率下，将水溶性引发剂加入到石蜡乳液中溶解并升温至65℃时开始缓慢滴加单体，继续升温至75-85℃，进行反应，单体滴加完成后保温2-4h，出料；3. Preparation of paraffin microcapsule emulsion: At a stirring rate of 500-1000 rpm, the water-soluble initiator is added to the paraffin emulsion to dissolve and the temperature is raised to 65 ° C, and the monomer is slowly added dropwise, and the temperature is further increased to 75- At 85 ° C, the reaction is carried out, and after the completion of the dropwise addition of the monomer, the temperature is maintained for 2-4 hours, and the discharge is performed;
4、后处理：真空抽滤，石油醚洗，水洗，在40-50℃真空干燥，气流粉碎机粉碎后得到石蜡微胶囊粉末。4. Post-treatment: vacuum filtration, petroleum ether washing, water washing, vacuum drying at 40-50 ° C, and pulverization by a jet mill to obtain paraffin microcapsule powder.
进一步地，配方中所述的石墨为天然鳞片石墨粒度为32-200目。Further, the graphite described in the formulation has a natural flake graphite particle size of 32-200 mesh.
进一步地，配方中所述的强酸为98％的浓硫酸，所述的强氧化剂为硝酸钠、高锰酸钾。Further, the strong acid described in the formulation is 98% concentrated sulfuric acid, and the strong oxidizing agent is sodium nitrate or potassium permanganate.
进一步地，石墨、浓硫酸、硝酸钠和高锰酸钾的质量比为1:(25-75):(0.5-1):(6-18)。Further, the mass ratio of graphite, concentrated sulfuric acid, sodium nitrate and potassium permanganate is 1: (25-75): (0.5-1): (6-18).
进一步地，配方中所述的石蜡为德国RUBITHERM产相变石蜡(相变点34℃、44℃与54℃)中的至少一种。Further, the paraffin wax described in the formulation is at least one of German RUBITHERM phase change paraffin wax (phase transition point 34 ° C, 44 ° C and 54 ° C).
进一步地，所述的非离子乳化剂包括吐温-80、吐温-60、司盘-80、司盘-60、OP-10中的一种或多种；阳离子型乳化剂包括十六烷基三甲基溴化铵、十二烷基氯化铵、溴化十六烷基吡啶中的至少一种。Further, the nonionic emulsifier comprises one or more of Tween-80, Tween-60, Span-80, Span-60, OP-10; the cationic emulsifier comprises hexadecane At least one of trimethylammonium bromide, dodecyl ammonium chloride, and cetylpyridinium bromide.
进一步地，所述的石蜡乳液中石蜡、非离子型乳化剂、阳离子型乳化剂及去离子水的质量比为1:0.08:0.04:12 Further, the mass ratio of the paraffin wax, the nonionic emulsifier, the cationic emulsifier and the deionized water in the paraffin emulsion is 1:0.08:0.04:12
进一步地，所述水溶性引发剂包括过硫酸铵、过硫酸钾、水溶性偶氮类引发剂中的至少一种。Further, the water-soluble initiator includes at least one of ammonium persulfate, potassium persulfate, and a water-soluble azo initiator.
进一步地，所述的单体为(甲基)丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸正辛酯、(甲基)丙烯酸、丙烯酸羟乙酯中的至少一种。Further, the monomer is methyl (meth)acrylate, ethyl methacrylate, butyl acrylate, isooctyl acrylate, lauryl methacrylate, n-octyl methacrylate, (meth)acrylic acid. And at least one of hydroxyethyl acrylate.
进一步地，所述的石蜡、单体、水溶性引发剂的质量比为1:1:0.02。Further, the mass ratio of the paraffin wax, the monomer, and the water-soluble initiator is 1:1:0.02.
本发明具有以下有益效果：利用本发明制备的微胶囊材料克服了目前微胶囊产品存在的壁材强度差、导热效率低、包裹效率及相变潜热低等种种不足，通过氧化石墨烯表面多种含氧基团与聚合物反应，提高了石蜡微胶囊相变材料的热稳定性、导热性、延长了使用寿命，且制备工艺简单，环保，所得到的石蜡相变微胶囊的相变材料粒径均匀，相变潜热可达160J/g，在建筑节能、保温产品、地暖等领域具有显著性能优势和良好的市场前景。The invention has the following beneficial effects: the microcapsule material prepared by the invention overcomes various shortcomings such as poor wall strength, low heat conduction efficiency, low package efficiency and low latent heat of phase change existing in the microcapsule product, and has various kinds of surface through graphene oxide. The reaction of the oxygen-containing group with the polymer improves the thermal stability and thermal conductivity of the paraffin microcapsule phase change material, prolongs the service life, and has a simple preparation process and environmental protection, and the obtained phase change material particle of the paraffin phase change microcapsule Uniform diameter, latent heat of phase change up to 160J/g, with significant performance advantages and good market prospects in the fields of building energy conservation, insulation products and floor heating.
附图说明DRAWINGS
图1为氧化石墨烯改性石蜡微胶囊相变材料的SEM图像。1 is an SEM image of a graphene oxide modified paraffin microcapsule phase change material.
图2为氧化石墨烯改性的石蜡微胶囊相变材料的DSC热焓测试曲线。2 is a DSC enthalpy test curve of a graphene oxide modified paraffin microcapsule phase change material.
具体实施方式detailed description
为了使本发明的目的、技术方案和有点更加清楚明白，以下结合具体实施例，对发明进行进一步详细说明，此处所描述的具体实施例仅仅用于解释本发明，并不用于限定本发明。The invention is further described in detail with reference to the preferred embodiments of the invention.
实施例1：Example 1:
在磁力搅拌器上，在低温(0-4℃)冰水浴，加入38目石墨1g、98％浓硫酸及硝酸钠、高锰酸钾，其中石墨：浓硫酸：硝酸钠： 高锰酸钾＝1:50:0.6:6，对石墨进行初步氧化；中温(35-40℃)水浴，逐次缓慢加入高锰酸钾，其中石墨：高锰酸钾＝1:6，保持搅拌；高温(80-90℃)水浴，完成对石墨的深度氧化，其中石墨：高锰酸钾＝1:3；加入去离子水，石墨：去离子水＝1:60，水解反应之后，加入30Vol％过氧化氢中和未反应的高锰酸钾，以溶液呈亮黄色后加入10Vol％的盐酸溶液，其中30Vol％过氧化氢：10Vol％的盐酸＝1:1.5，真空抽滤，用去离子水洗涤至pH值为7，经60℃干燥、研磨得到氧化石墨烯。一边搅拌，一边将制备的氧化石墨烯加入到去离子水中，超声分散1h左右，得到3％的氧化石墨烯溶液待用。在搅拌釜中加入34℃石蜡、吐温-80、司本-80和十六烷基三甲基溴化铵，升高温度至65℃，缓慢加入在去离子水中分散好的石墨(34℃石蜡：吐温-80：司本-80：十六烷基三甲基溴化铵：石墨分散液＝1:0.06:0.02：0.04:12)，在500r/min搅拌速度下搅拌0.5h，得到O/W型石蜡乳液。在500转/分钟的搅拌速率下，将过硫酸铵加入到石蜡乳液中溶解并升温至65℃时开始缓慢滴加混合单体(石蜡：甲基丙烯酸甲酯：丙烯酸丁酯：过硫酸铵＝1:0.8:0.2:0.02)，继续升温至75℃，进行反应，单体滴加完成后保温2h，出料，真空抽滤，石油醚洗，水洗，在40-50℃真空干燥，气流粉碎机粉碎后得到氧化石墨烯改性石蜡微胶囊粉末。On a magnetic stirrer, in a low temperature (0-4 ° C) ice water bath, add 38 mesh graphite 1 g, 98% concentrated sulfuric acid and sodium nitrate, potassium permanganate, of which graphite: concentrated sulfuric acid: sodium nitrate: Potassium permanganate = 1:50:0.6:6, preliminary oxidation of graphite; medium temperature (35-40 ° C) water bath, slowly added potassium permanganate, graphite: potassium permanganate = 1:6, keep stirring High temperature (80-90 ° C) water bath to complete the deep oxidation of graphite, in which graphite: potassium permanganate = 1:3; deionized water, graphite: deionized water = 1:60, after hydrolysis, add 30Vol % hydrogen peroxide neutralized unreacted potassium permanganate. After the solution was bright yellow, add 10 Vol% hydrochloric acid solution, 30 Vol% hydrogen peroxide: 10 Vol% hydrochloric acid = 1:1.5, vacuum filtered, deionized The water was washed to a pH of 7, and dried by grinding at 60 ° C to obtain graphene oxide. The prepared graphene oxide was added to deionized water while stirring, and ultrasonically dispersed for about 1 hour to obtain a 3% graphene oxide solution to be used. Add 34 ° C paraffin, Tween-80, Siben-80 and cetyltrimethylammonium bromide to the stirred tank, raise the temperature to 65 ° C, slowly add the graphite dispersed in deionized water (34 ° C Paraffin: Tween-80: Siben-80: Cetyltrimethylammonium bromide: graphite dispersion = 1: 0.06: 0.02: 0.04: 12), stirred at 500 r / min stirring speed for 0.5 h, O/W paraffin emulsion. At a stirring rate of 500 rpm, ammonium persulfate was added to the paraffin emulsion to dissolve and the temperature was raised to 65 ° C. The mixed monomer was slowly added dropwise (paraffin: methyl methacrylate: butyl acrylate: ammonium persulfate = 1:0.8:0.2:0.02), continue to raise the temperature to 75 ° C, carry out the reaction, the monomer is added after the completion of the addition of 2 h, discharge, vacuum filtration, petroleum ether washing, water washing, vacuum drying at 40-50 ° C, jet pulverization After the machine was pulverized, a graphene oxide-modified paraffin microcapsule powder was obtained.
实施例2：Example 2:
在磁力搅拌器上，在低温(0-4℃)冰水浴，加入50目石墨1g、98％浓硫酸及硝酸钠、高锰酸钾，其中石墨：浓硫酸：硝酸钠：高锰酸钾＝1:60:1:3，对石墨进行初步氧化；中温(35-40℃)水浴，逐次缓慢加入高锰酸钾，其中石墨：高锰酸钾＝1:3，保持搅拌；高温(80-90℃)水浴，完成对石墨的深度氧化，其中石墨：高锰酸钾＝1:3；加入去离子水，石墨：去离子水＝1:70，水解反应之后，加入 30Vol％过氧化氢中和未反应的高锰酸钾，以溶液呈亮黄色后加入10Vol％的盐酸溶液，其中30Vol％过氧化氢：10Vol％的盐酸＝1:2，真空抽滤，用去离子水洗涤至pH值为7，经60℃干燥、研磨得到氧化石墨烯。一边搅拌，一边将制备的氧化石墨烯加入到去离子水中，超声分散1h左右，得到2％的氧化石墨烯溶液待用。在搅拌釜中加入44℃石蜡、吐温-80、司本-80和十六烷基三甲基溴化铵，升高温度至65℃，缓慢加入在去离子水中分散好的石墨(34℃石蜡：吐温-80：司本-80：十六烷基三甲基溴化铵：石墨分散液＝1:0.06:0.02：0.04:12)，在500r/min搅拌速度下搅拌0.5h，得到O/W型石蜡乳液。在500转/分钟的搅拌速率下，将过硫酸铵加入到石蜡乳液中溶解并升温至65℃时开始缓慢滴加混合单体(石蜡：甲基丙烯酸甲酯：丙烯酸丁酯：过硫酸铵＝1:0.8:0.2:0.02)，继续升温至75℃，进行反应，单体滴加完成后保温2h，出料，真空抽滤，石油醚洗，水洗，在40-50℃真空干燥，气流粉碎机粉碎后得到氧化石墨烯改性石蜡微胶囊粉末。On a magnetic stirrer, in a low temperature (0-4 ° C) ice water bath, add 50 g of graphite 1 g, 98% concentrated sulfuric acid and sodium nitrate, potassium permanganate, of which graphite: concentrated sulfuric acid: sodium nitrate: potassium permanganate = 1:60:1:3, preliminary oxidation of graphite; medium temperature (35-40 ° C) water bath, slowly add potassium permanganate slowly, of which graphite: potassium permanganate = 1:3, keep stirring; high temperature (80- 90 ° C) water bath, complete the deep oxidation of graphite, where graphite: potassium permanganate = 1:3; add deionized water, graphite: deionized water = 1: 70, after hydrolysis reaction, add 30Vol% hydrogen peroxide neutralized unreacted potassium permanganate. After the solution was bright yellow, add 10Vol% hydrochloric acid solution, 30Vol% hydrogen peroxide: 10Vol% hydrochloric acid=1:2, vacuum filtration, use The ionized water was washed to a pH of 7, and dried and ground at 60 ° C to obtain graphene oxide. The prepared graphene oxide was added to deionized water while stirring, and ultrasonically dispersed for about 1 hour to obtain a 2% graphene oxide solution to be used. Add 44 ° C paraffin, Tween-80, Si Ben-80 and cetyltrimethylammonium bromide to the stirred tank, raise the temperature to 65 ° C, slowly add the graphite dispersed in deionized water (34 ° C Paraffin: Tween-80: Siben-80: Cetyltrimethylammonium bromide: graphite dispersion = 1: 0.06: 0.02: 0.04: 12), stirred at 500 r / min stirring speed for 0.5 h, O/W paraffin emulsion. At a stirring rate of 500 rpm, ammonium persulfate was added to the paraffin emulsion to dissolve and the temperature was raised to 65 ° C. The mixed monomer was slowly added dropwise (paraffin: methyl methacrylate: butyl acrylate: ammonium persulfate = 1:0.8:0.2:0.02), continue to raise the temperature to 75 ° C, carry out the reaction, the monomer is added after the completion of the addition of 2 h, discharge, vacuum filtration, petroleum ether washing, water washing, vacuum drying at 40-50 ° C, jet pulverization After the machine was pulverized, a graphene oxide-modified paraffin microcapsule powder was obtained.
实施例3：Example 3:
在磁力搅拌器上，在低温(0-4℃)冰水浴，加入200目石墨1g、98％浓硫酸及硝酸钠、高锰酸钾，其中石墨：浓硫酸：硝酸钠：高锰酸钾＝1:70:0.5:3，对石墨进行初步氧化；中温(35-40℃)水浴，逐次缓慢加入高锰酸钾，其中石墨：高锰酸钾＝1:3，保持搅拌；高温(80-90℃)水浴，完成对石墨的深度氧化，其中石墨：高锰酸钾＝1:3；加入去离子水，石墨：去离子水＝1:80，水解反应之后，加入30Vol％过氧化氢中和未反应的高锰酸钾，以溶液呈亮黄色后加入10Vol％的盐酸溶液，其中30Vol％过氧化氢：10Vol％的盐酸＝1:2，真空抽滤，用去离子水洗涤至pH值为7，经60℃干燥、研磨得到氧化石墨烯。一边搅拌，一边将制备的氧化石墨烯加入到去离子水 中，超声分散1h左右，得到2％的氧化石墨烯溶液待用。在搅拌釜中加入44℃石蜡、吐温-60、司本-60和十二烷基氯化铵，升高温度至75℃，缓慢加入在去离子水中分散好的石墨(44℃石蜡：吐温-60：司本-60：十二烷基氯化铵：石墨分散液＝1:0.05:0.03：0.04:12)，在500r/min搅拌速度下搅拌0.5h，得到O/W型石蜡乳液。在500转/分钟的搅拌速率下，将过硫酸钾加入到石蜡乳液中溶解并升温至65℃时开始缓慢滴加混合单体(石蜡：丙烯酸：丙烯酸甲酯：丙烯酸丁酯：过硫酸铵＝1:0.2:0.6:0.2:0.02)，继续升温至75℃，进行反应，单体滴加完成后保温2h，出料，真空抽滤，石油醚洗，水洗，在40-50℃真空干燥，气流粉碎机粉碎后得到氧化石墨烯改性石蜡微胶囊粉末。On a magnetic stirrer, in a low temperature (0-4 ° C) ice water bath, add 200 g of graphite 1 g, 98% concentrated sulfuric acid and sodium nitrate, potassium permanganate, of which graphite: concentrated sulfuric acid: sodium nitrate: potassium permanganate = 1:70:0.5:3, preliminary oxidation of graphite; medium temperature (35-40 ° C) water bath, slowly add potassium permanganate slowly, of which graphite: potassium permanganate = 1:3, keep stirring; high temperature (80- 90 ° C) water bath, complete the deep oxidation of graphite, where graphite: potassium permanganate = 1:3; adding deionized water, graphite: deionized water = 1: 80, after hydrolysis, adding 30Vol% hydrogen peroxide And unreacted potassium permanganate, after the solution is bright yellow, add 10Vol% hydrochloric acid solution, 30Vol% hydrogen peroxide: 10Vol% hydrochloric acid = 1:2, vacuum filtration, wash with deionized water to pH 7, dried at 60 ° C, ground to obtain graphene oxide. The prepared graphene oxide is added to the deionized water while stirring In the middle, the ultrasonic dispersion is about 1 h, and a 2% graphene oxide solution is obtained for use. Add 44 ° C paraffin, Tween-60, Siben-60 and lauryl ammonium chloride to the stirred tank, raise the temperature to 75 ° C, slowly add the graphite dispersed in deionized water (44 ° C paraffin: spit Wen-60: Siben-60: lauryl ammonium chloride: graphite dispersion = 1:0.05:0.03:0.04:12), stirred at 500r/min stirring speed for 0.5h to obtain O/W paraffin emulsion . At a stirring rate of 500 rpm, potassium persulfate was added to the paraffin emulsion to dissolve and heated to 65 ° C. The mixed monomer was slowly added dropwise (paraffin: acrylic acid: methyl acrylate: butyl acrylate: ammonium persulfate = 1:0.2:0.6:0.2:0.02), continue to raise the temperature to 75 ° C, carry out the reaction, the monomer is added after the completion of the addition of 2 h, discharge, vacuum filtration, petroleum ether washing, water washing, vacuum drying at 40-50 ° C, After the jet mill was pulverized, graphene oxide-modified paraffin microcapsule powder was obtained.
实施例4：Example 4:
在磁力搅拌器上，在低温(0-4℃)冰水浴，加入200目石墨1g、98％浓硫酸及硝酸钠、高锰酸钾，其中石墨：浓硫酸：硝酸钠：高锰酸钾＝1:75:0.5:6，对石墨进行初步氧化；中温(35-40℃)水浴，逐次缓慢加入高锰酸钾，其中石墨：高锰酸钾＝1:6，保持搅拌；高温(80-90℃)水浴，完成对石墨的深度氧化，其中石墨：高锰酸钾＝1:6；加入去离子水，石墨：去离子水＝1:80，水解反应之后，加入30Vol％过氧化氢中和未反应的高锰酸钾，以溶液呈亮黄色后加入10Vol％的盐酸溶液，其中30Vol％过氧化氢：10Vol％的盐酸＝1:2，真空抽滤，用去离子水洗涤至pH值为7，经60℃干燥、研磨得到氧化石墨烯。一边搅拌，一边将制备的氧化石墨烯加入到去离子水中，超声分散1h左右，得到3％的氧化石墨烯溶液待用。在搅拌釜中加入54℃石蜡、吐温-60、司本-60和溴化十六烷基吡啶，升高温度至75℃，缓慢加入在去离子水中分散好的石墨(44℃石蜡：吐温-60：司本-60：溴化十六烷基吡啶：石墨分散液＝1:0.05:0.03： 0.04:12)，在500r/min搅拌速度下搅拌0.5h，得到O/W型石蜡乳液。在500转/分钟的搅拌速率下，将过硫酸钾加入到石蜡乳液中溶解并升温至65℃时开始缓慢滴加混合单体(石蜡：甲基丙烯酸甲酯：丙烯酸甲酯：甲基丙烯酸：丙烯酸异辛酯：过硫酸铵＝1:0.3:0.4:0.1:0.2:0.02)，继续升温至75℃，进行反应，单体滴加完成后保温2h，出料，真空抽滤，石油醚洗，水洗，在40-50℃真空干燥，气流粉碎机粉碎后得到氧化石墨烯改性石蜡微胶囊粉末。On a magnetic stirrer, in a low temperature (0-4 ° C) ice water bath, add 200 g of graphite 1 g, 98% concentrated sulfuric acid and sodium nitrate, potassium permanganate, of which graphite: concentrated sulfuric acid: sodium nitrate: potassium permanganate = 1:75:0.5:6, preliminary oxidation of graphite; medium temperature (35-40 °C) water bath, slowly add potassium permanganate slowly, wherein graphite: potassium permanganate = 1:6, keep stirring; high temperature (80- 90 ° C) water bath, complete the deep oxidation of graphite, where graphite: potassium permanganate = 1:6; adding deionized water, graphite: deionized water = 1:80, after hydrolysis, adding 30Vol% hydrogen peroxide And unreacted potassium permanganate, after the solution is bright yellow, add 10Vol% hydrochloric acid solution, 30Vol% hydrogen peroxide: 10Vol% hydrochloric acid = 1:2, vacuum filtration, wash with deionized water to pH 7, dried at 60 ° C, ground to obtain graphene oxide. The prepared graphene oxide was added to deionized water while stirring, and ultrasonically dispersed for about 1 hour to obtain a 3% graphene oxide solution to be used. Add 54 ° C paraffin, Tween-60, Siben-60 and cetylpyridinium bromide to the stirred tank, raise the temperature to 75 ° C, slowly add the graphite dispersed in deionized water (44 ° C paraffin: spit Wen-60: Siben-60: cetylpyridinium bromide: graphite dispersion = 1:0.05:0.03: 0.04:12), stirring at a stirring speed of 500 r/min for 0.5 h to obtain an O/W type paraffin emulsion. At a stirring rate of 500 rpm, potassium persulfate was added to the paraffin emulsion to dissolve and the temperature was raised to 65 ° C, and the mixed monomer was slowly added dropwise (paraffin: methyl methacrylate: methyl acrylate: methacrylic acid: Isooctyl acrylate: ammonium persulfate = 1:0.3:0.4:0.1:0.2:0.02), continue to raise the temperature to 75 ° C, carry out the reaction, the monomer is added after the completion of the addition of 2 h, discharge, vacuum filtration, petroleum ether wash , washing with water, drying at 40-50 ° C under vacuum, pulverizing by a jet mill to obtain graphene oxide modified paraffin microcapsule powder.
实施例5：Example 5:
在磁力搅拌器上，在低温(0-4℃)冰水浴，加入200目石墨1g、98％浓硫酸及硝酸钠、高锰酸钾，其中石墨：浓硫酸：硝酸钠：高锰酸钾＝1:50:0.5:2，对石墨进行初步氧化；中温(35-40℃)水浴，逐次缓慢加入高锰酸钾，其中石墨：高锰酸钾＝1:2，保持搅拌；高温(80-90℃)水浴，完成对石墨的深度氧化，其中石墨：高锰酸钾＝1:2；加入去离子水，石墨：去离子水＝1:80，水解反应之后，加入30Vol％过氧化氢中和未反应的高锰酸钾，以溶液呈亮黄色后加入10Vol％的盐酸溶液，其中30Vol％过氧化氢：10Vol％的盐酸＝1:2，真空抽滤，用去离子水洗涤至pH值为7，经60℃干燥、研磨得到氧化石墨烯。一边搅拌，一边将制备的氧化石墨烯加入到去离子水中，超声分散1h左右，得到3％的氧化石墨烯溶液待用。在搅拌釜中加入54℃石蜡、吐温-60、司本-60和十二烷基氯化铵，升高温度至75℃，缓慢加入在去离子水中分散好的石墨(44℃石蜡：吐温-60：司本-60：十二烷基氯化铵：石墨分散液＝1:0.05:0.03：0.04:12)，在500r/min搅拌速度下搅拌0.5h，得到O/W型石蜡乳液。在500转/分钟的搅拌速率下，将过硫酸钾加入到石蜡乳液中溶解并升温至65℃时开始缓慢滴加混合单体(石蜡：甲基丙烯酸甲酯：丙烯酸甲酯：丙烯酸异辛酯：过硫酸铵＝1:0.3:0.5:0.2:0.02)，继续升温至 75℃，进行反应，单体滴加完成后保温2h，出料，真空抽滤，石油醚洗，水洗，在40-50℃真空干燥，气流粉碎机粉碎后得到氧化石墨烯改性石蜡微胶囊粉末。On a magnetic stirrer, in a low temperature (0-4 ° C) ice water bath, add 200 g of graphite 1 g, 98% concentrated sulfuric acid and sodium nitrate, potassium permanganate, of which graphite: concentrated sulfuric acid: sodium nitrate: potassium permanganate = 1:50:0.5:2, preliminary oxidation of graphite; medium temperature (35-40 ° C) water bath, slowly add potassium permanganate slowly, of which graphite: potassium permanganate = 1:2, keep stirring; high temperature (80- 90 ° C) water bath, complete the deep oxidation of graphite, where graphite: potassium permanganate = 1: 2; adding deionized water, graphite: deionized water = 1: 80, after hydrolysis, adding 30Vol% hydrogen peroxide And unreacted potassium permanganate, after the solution is bright yellow, add 10Vol% hydrochloric acid solution, 30Vol% hydrogen peroxide: 10Vol% hydrochloric acid = 1:2, vacuum filtration, wash with deionized water to pH 7, dried at 60 ° C, ground to obtain graphene oxide. The prepared graphene oxide was added to deionized water while stirring, and ultrasonically dispersed for about 1 hour to obtain a 3% graphene oxide solution to be used. Add 54 ° C paraffin, Tween-60, Siben-60 and lauryl ammonium chloride to the stirred tank, raise the temperature to 75 ° C, slowly add the graphite dispersed in deionized water (44 ° C paraffin: spit Wen-60: Siben-60: lauryl ammonium chloride: graphite dispersion = 1:0.05:0.03:0.04:12), stirred at 500r/min stirring speed for 0.5h to obtain O/W paraffin emulsion . At a stirring rate of 500 rpm, potassium persulfate was added to the paraffin emulsion to dissolve and the temperature was raised to 65 ° C. The mixed monomer was slowly added dropwise (paraffin: methyl methacrylate: methyl acrylate: isooctyl acrylate) : ammonium persulfate = 1:0.3:0.5:0.2:0.02), continue to heat up to At 75 ° C, the reaction is carried out, the monomer is added and the temperature is kept for 2 hours, the material is discharged, vacuum filtration, petroleum ether washing, water washing, vacuum drying at 40-50 ° C, and pulverization by a jet mill to obtain graphene oxide modified paraffin microcapsules. powder.
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，本领域普通技术人员对本发明的技术方案所做的其他修改或者等同替换，只要不脱离本发明技术方案的精神和范围，均应涵盖在本发明的权利要求范围当中。 The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to be limiting, and other modifications or equivalents of the technical solutions of the present invention will be made by those skilled in the art without departing from the spirit and scope of the present invention. The scope is intended to be included within the scope of the appended claims.

Claims (10)

  1. 一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，包括以下步骤：A method for preparing a graphene oxide modified paraffin microcapsule phase change material, comprising the steps of:
    (1)氧化石墨烯的制备：在磁力搅拌器上，低温冰水浴，所述低温冰水浴的温度在0-4℃，搅拌速度为300-500rpm，反应时间为1.5h，向其中加入石墨、浓酸及强氧化剂，对石墨进行初步氧化；中温水浴，所述中温水浴温度在35-40℃，搅拌速度为300-500rpm，反应时间为2h，再逐次缓慢加入高锰酸钾，所述高锰酸钾分三次加入，在低温初步氧化阶段加入1/3，在中温氧化阶段，分两次加入剩余的高锰酸钾，保持搅拌；高温水浴，所述高温水浴温度在80-90℃，搅拌速度为300-500rpm，反应时间为4h，完成对石墨的深度氧化；加入去离子水，其中石墨与去离子水的质量比为1:(60-80)，水解反应之后，加入30Vol％过氧化氢中和未反应的高锰酸钾，以溶液呈亮黄色为终点，然后加入10Vol％的盐酸溶液，30Vol％过氧化氢与10Vol％盐酸的质量比为1:(1.5-2)，真空抽滤，用去离子水洗涤至pH值为7，经60℃干燥、研磨得到氧化石墨烯，将制备的氧化石墨烯加入到去离子水中，超声分散1h左右，得到1-5％的氧化石墨烯溶液待用；(1) Preparation of graphene oxide: on a magnetic stirrer, a low temperature ice water bath, the temperature of the low temperature ice water bath is 0-4 ° C, the stirring speed is 300-500 rpm, the reaction time is 1.5 h, and graphite is added thereto. Concentrated acid and strong oxidant, preliminary oxidation of graphite; medium temperature water bath, the temperature of the medium temperature water bath is 35-40 ° C, the stirring speed is 300-500 rpm, the reaction time is 2 h, and then potassium permanganate is slowly added successively. The potassium permanganate is added in three portions, and 1/3 is added in the preliminary oxidation stage of low temperature. In the middle temperature oxidation stage, the remaining potassium permanganate is added in two portions to maintain stirring; the high temperature water bath is at a temperature of 80-90. °C, stirring speed is 300-500rpm, reaction time is 4h, complete deep oxidation of graphite; adding deionized water, wherein the mass ratio of graphite to deionized water is 1: (60-80), after hydrolysis reaction, add 30Vol % hydrogen peroxide neutralized unreacted potassium permanganate, the solution was bright yellow, and then added 10 Vol% hydrochloric acid solution, the mass ratio of 30 Vol% hydrogen peroxide to 10 Vol% hydrochloric acid was 1: (1.5-2) , vacuum filtration, washed with deionized water to pH 7, drying and grinding at 60 ° C to obtain graphene oxide, the prepared graphene oxide is added to deionized water, ultrasonic dispersion for about 1h, to obtain 1-5% of graphene oxide solution for use;
    (2)石蜡乳液的制备：在搅拌釜中加入石蜡、非离子乳化剂和离子型乳化剂，升高温度至65-75℃，加入在去离子水中分散好的石墨，在500-1000r/min搅拌速度下搅拌0.5-1h，得到O/W型石蜡乳液；(2) Preparation of paraffin emulsion: Paraffin, nonionic emulsifier and ionic emulsifier are added to the stirred tank, the temperature is raised to 65-75 ° C, and the graphite dispersed in deionized water is added at 500-1000 r/min. Stirring at a stirring speed for 0.5-1 h to obtain an O/W paraffin emulsion;
    (3)石蜡微胶囊乳液的制备：在500-1000转/分钟的搅拌速率下，将水溶性引发剂加入到石蜡乳液中溶解并升温至65℃时开始缓慢滴加单体，继续升温至75-85℃，进行反应，单体滴加完成后保温2-4h，出料； (3) Preparation of paraffin microcapsule emulsion: At a stirring rate of 500-1000 rpm, the water-soluble initiator is added to the paraffin emulsion to dissolve and the temperature is raised to 65 ° C, and the monomer is slowly added dropwise, and the temperature is further increased to 75. -85 ° C, the reaction is carried out, the monomer is added after the completion of the addition of 2-4 h, discharge;
    (4)后处理：真空抽滤，石油醚洗，水洗，在40-50℃真空干燥，气流粉碎机粉碎后得到石蜡微胶囊粉末。(4) Post-treatment: vacuum filtration, petroleum ether washing, water washing, vacuum drying at 40-50 ° C, and pulverization by a jet mill to obtain paraffin microcapsule powder.
  2. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，配方中所述的石墨为天然鳞片石墨粒度为32-200目。The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the graphite in the formulation has a natural flake graphite particle size of 32-200 mesh.
  3. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，配方中所述的强酸为98％的浓硫酸，所述的强氧化剂为硝酸钠、高锰酸钾。The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the strong acid in the formulation is 98% concentrated sulfuric acid, and the strong oxidant is sodium nitrate. potassium permanganate.
  4. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，石墨、浓硫酸、硝酸钠和高锰酸钾的质量比为1:(25-75):(0.5-1):(6-18)。The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the mass ratio of graphite, concentrated sulfuric acid, sodium nitrate and potassium permanganate is 1: (25-75) ): (0.5-1): (6-18).
  5. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，配方中所述的石蜡为德国RUBITHERM产相变石蜡(相变点34℃、44℃与54℃)中的至少一种。The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the paraffin wax in the formula is a phase change paraffin wax produced by RUBITHERM in Germany (phase change point 34 ° C, 44 ° C) At least one of with 54 ° C).
  6. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，所述的非离子乳化剂包括吐温-80、吐温-60、司盘-80、司盘-60、OP-10中的一种或多种；阳离子型乳化剂包括十六烷基三甲基溴化铵、十二烷基氯化铵、溴化十六烷基吡啶中的至少一种。The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the nonionic emulsifier comprises Tween-80, Tween-60, and Span-80 One or more of Span-60, OP-10; cationic emulsifiers include cetyltrimethylammonium bromide, dodecyl ammonium chloride, cetylpyridinium bromide At least one.
  7. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，所述的石蜡乳液中石蜡、非离子型乳化剂、阳离子型乳化剂及去离子水的质量比为1:0.08:0.04:12The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the paraffin emulsion is a paraffin wax, a nonionic emulsifier, a cationic emulsifier and deionized water. The mass ratio is 1:0.08:0.04:12
  8. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，所述水溶性引发剂包括过硫酸铵、过硫酸钾、水溶性偶氮类引发剂中的至少一种。 The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the water-soluble initiator comprises ammonium persulfate, potassium persulfate, and a water-soluble azo initiator. At least one of them.
  9. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，所述的单体为(甲基)丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸正辛酯、(甲基)丙烯酸、丙烯酸羟乙酯中的至少一种。The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the monomer is methyl (meth) acrylate, ethyl methacrylate or butyl acrylate. At least one of an ester, isooctyl acrylate, lauryl methacrylate, n-octyl methacrylate, (meth)acrylic acid, or hydroxyethyl acrylate.
  10. 根据权利要求1所述的一种氧化石墨烯改性石蜡微胶囊相变材料的制备方法，其特征在于，所述的石蜡、单体、水溶性引发剂的质量比为1:1:0.02。 The method for preparing a graphene oxide modified paraffin microcapsule phase change material according to claim 1, wherein the mass ratio of the paraffin wax, the monomer, and the water-soluble initiator is 1:1:0.02.
PCT/CN2014/087800 2014-08-30 2014-09-29 Method for preparing paraffin microcapsule phase-change material modified by graphene oxide WO2016029527A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410435848.7A CN104212416B (en) 2014-08-30 2014-08-30 Preparation method for paraffin microcapsule phase-change material modified by graphene oxide
CN201410435848.7 2014-08-30

Publications (1)

Publication Number Publication Date
WO2016029527A1 true WO2016029527A1 (en) 2016-03-03

Family

ID=52094332

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/087800 WO2016029527A1 (en) 2014-08-30 2014-09-29 Method for preparing paraffin microcapsule phase-change material modified by graphene oxide

Country Status (2)

Country Link
CN (1) CN104212416B (en)
WO (1) WO2016029527A1 (en)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109824036A (en) * 2019-03-29 2019-05-31 北海艾米碳材料技术研发有限公司 The method of high temperature cabonization solid Carbon Materials graphene
CN111693483A (en) * 2020-06-16 2020-09-22 青岛海关技术中心 Detection method of finishing auxiliary for functional textiles
CN111793989A (en) * 2020-07-27 2020-10-20 山东三采秀纺织科技有限公司 Dyeing and finishing method for spandex fabric of mint-fragrant cool regenerated cellulose fiber
CN112121738A (en) * 2020-09-28 2020-12-25 杭州应星新材料有限公司 Preparation method of functionalized microcapsule and functionalized microcapsule prepared by preparation method
CN112375392A (en) * 2020-11-25 2021-02-19 德阳中碳新材料科技有限公司 Preparation method of graphene heat-conducting interface material
CN112588214A (en) * 2020-12-23 2021-04-02 西北工业大学 Phase-change material microcapsule with photo-thermal conversion and energy storage properties and preparation method thereof
CN112742316A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Preparation method of phase change microcapsule material
CN113214884A (en) * 2021-04-20 2021-08-06 清华大学 Preparation method of super-regular graphene-based lubricating grease
CN113385161A (en) * 2021-07-02 2021-09-14 青岛瑞利特新材料科技有限公司 Formaldehyde removal material of graphene nano composite gel and preparation process
CN113861942A (en) * 2021-09-14 2021-12-31 中北大学 Organic-microcapsule phase change material, preparation method thereof and application thereof in battery thermal management system
CN114181532A (en) * 2021-12-22 2022-03-15 仲恺农业工程学院 Phase-change heat-conducting silicone grease containing macromolecular modifier and preparation method thereof
CN114709083A (en) * 2022-05-25 2022-07-05 深圳市今朝时代股份有限公司 Modified graphene composite material and supercapacitor
CN114873955A (en) * 2022-04-24 2022-08-09 四川衡鼎建材有限公司 Concrete capable of recycling waste and preparation process thereof
CN114989786A (en) * 2022-06-09 2022-09-02 纯钧新材料(深圳)有限公司 Salin resin phase-change microcapsule and preparation method thereof
CN115010538A (en) * 2022-05-07 2022-09-06 山西粮缘金土地科技股份有限公司 Two-component composite microorganism water-retention temperature-control slow-release fertilizer and preparation method and application thereof
CN115043637A (en) * 2022-05-20 2022-09-13 邢台建德水泥有限公司 Cement containing biomass combustion waste material and preparation method thereof
CN115073075A (en) * 2022-05-10 2022-09-20 中建西部建设北方有限公司 Super-long structure high-crack-resistance compensation shrinkage concrete and preparation method thereof
WO2022262103A1 (en) * 2021-06-15 2022-12-22 南通大学 Microcapsule having both infrared and radar stealth, preparation method therefor and application thereof
CN115652464A (en) * 2022-10-10 2023-01-31 南通强生新材料科技股份有限公司 Graphene extremely-cold-resistant gloves and preparation method thereof
CN116019962A (en) * 2022-11-23 2023-04-28 武汉中科先进材料科技有限公司 Antibacterial microcapsule, preparation method thereof, long-acting antibacterial dressing and application
CN116063996A (en) * 2023-04-03 2023-05-05 西南石油大学 Phase-change heat storage microcapsule material suitable for cooling drilling fluid and preparation method thereof
CN116350727A (en) * 2022-12-27 2023-06-30 北京蜜蜂堂生物医药股份有限公司 Beeswax paste for wax therapy and preparation method thereof
CN117534946A (en) * 2024-01-10 2024-02-09 上海沪正实业有限公司 Nanometer microcapsule heat insulation function master batch and preparation method thereof
CN117601456A (en) * 2024-01-22 2024-02-27 四川省宜宾普什建材有限责任公司 Processing technology of large-caliber electric melting type plastic pipe fitting

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104861934A (en) * 2015-05-26 2015-08-26 西南科技大学 Preparation method of phase change microcapsule with graphene-modified wall material
CN104877642A (en) * 2015-06-15 2015-09-02 南京工业大学 Phase-change microcapsule composition material and preparation method thereof
CN105348797B (en) * 2015-10-21 2018-04-13 中国科学院宁波材料技术与工程研究所 A kind of graphene-based heat conductive silica gel phase change composite material and preparation method thereof
CN105860936A (en) * 2016-04-08 2016-08-17 吉林建筑大学 Graphene oxide disperse composite phase-change energy storage microcapsules and preparation method
CN106010458B (en) * 2016-06-03 2018-12-21 大连理工大学 A kind of magnetic heat-photo-thermal is double to drive energy conversion and the polymer nanocomposite composite phase-change energy storage material of storage and preparation method thereof
CN105969317B (en) * 2016-06-07 2019-09-03 四川大学 A kind of Lauxite paraffin microcapsule material and preparation method with the high enthalpy of high heat conductance
CN106433567A (en) * 2016-10-26 2017-02-22 南通聚仁新材料科技有限公司 Double-coated paraffin microcapsule phase change material and preparation method thereof
CN106732222A (en) * 2017-03-24 2017-05-31 天津双君智材科技发展有限公司 Pitch crack autogenous healing microcapsules and preparation method thereof
CN107417867B (en) * 2017-06-13 2020-02-14 陕西科技大学 Preparation method of graphene oxide modified composite phase change microcapsule
CN107539984A (en) * 2017-10-19 2018-01-05 苏州方卓材料科技有限公司 The preparation method of graphite material
CN109251732A (en) * 2018-09-17 2019-01-22 南通和清纺织科技有限公司 A kind of preparation method of graphene microcapsules fiber
CN111518518A (en) * 2020-04-30 2020-08-11 江苏可米新材料科技有限公司 Multi-wall graphene oxide phase-change microcapsule material and preparation method thereof
CN111411415A (en) * 2020-05-08 2020-07-14 深圳天元羲王材料科技有限公司 Graphene modified flexible polyester
CN111851079B (en) * 2020-07-27 2022-12-20 山东三采秀纺织科技有限公司 Microencapsulated wormwood essential oil-containing mosquito-repellent fabric finishing agent and mosquito-repellent fabric finishing method
CN111849424B (en) * 2020-08-05 2021-09-21 哈尔滨工业大学 Phase-change heat storage material with microsphere structure and preparation method thereof
CN112251196A (en) * 2020-09-11 2021-01-22 南昌大学 Temperature and humidity regulating material of sepiolite-zeolite powder doped microcapsule and preparation method thereof
CN113845885A (en) * 2021-09-23 2021-12-28 华北理工大学 Low-temperature phase change composite material and preparation method thereof
CN114029009A (en) * 2021-11-22 2022-02-11 哈尔滨工业大学 Preparation method of high-efficiency and environment-friendly graphene-paraffin phase-change microcapsule material
CN114783783B (en) * 2022-05-17 2023-08-18 武夷学院 Preparation method of nitrogen-sulfur co-doped graphene-based composite porous aerogel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013012907A2 (en) * 2011-07-18 2013-01-24 University Of South Florida Method of encapsulating a phase change material with a metal oxide
US20130308279A1 (en) * 2012-05-15 2013-11-21 Gerald Ho Kim Thermal Energy Storage With A Phase-Change Material In A Non-Metal Container
CN103752234A (en) * 2014-01-07 2014-04-30 同济大学 Preparation method of oxidized graphene phase change microcapsule
CN104001458A (en) * 2014-06-16 2014-08-27 深圳市优能橡塑制品股份有限公司 Phase-change thermoregulation microcapsule and preparing method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101670256B (en) * 2009-09-28 2011-12-28 清华大学 Preparation method of phase change material microcapsule
CN103212351B (en) * 2013-04-09 2015-03-11 北京汽车新能源汽车有限公司 Preparation and application methods of high-heat-conductivity flame retardant phase change microcapsule

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013012907A2 (en) * 2011-07-18 2013-01-24 University Of South Florida Method of encapsulating a phase change material with a metal oxide
US20130308279A1 (en) * 2012-05-15 2013-11-21 Gerald Ho Kim Thermal Energy Storage With A Phase-Change Material In A Non-Metal Container
CN103752234A (en) * 2014-01-07 2014-04-30 同济大学 Preparation method of oxidized graphene phase change microcapsule
CN104001458A (en) * 2014-06-16 2014-08-27 深圳市优能橡塑制品股份有限公司 Phase-change thermoregulation microcapsule and preparing method thereof

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109824036A (en) * 2019-03-29 2019-05-31 北海艾米碳材料技术研发有限公司 The method of high temperature cabonization solid Carbon Materials graphene
CN112742316A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Preparation method of phase change microcapsule material
CN112742316B (en) * 2019-10-31 2023-07-28 中国石油化工股份有限公司 Preparation method of phase-change microcapsule material
CN111693483A (en) * 2020-06-16 2020-09-22 青岛海关技术中心 Detection method of finishing auxiliary for functional textiles
CN111793989A (en) * 2020-07-27 2020-10-20 山东三采秀纺织科技有限公司 Dyeing and finishing method for spandex fabric of mint-fragrant cool regenerated cellulose fiber
CN111793989B (en) * 2020-07-27 2022-12-20 山东三采秀纺织科技有限公司 Dyeing and finishing method for spandex fabric of mint-fragrant cool regenerated cellulose fiber
CN112121738A (en) * 2020-09-28 2020-12-25 杭州应星新材料有限公司 Preparation method of functionalized microcapsule and functionalized microcapsule prepared by preparation method
CN112121738B (en) * 2020-09-28 2021-08-31 杭州应星新材料有限公司 Preparation method of functionalized microcapsule and functionalized microcapsule prepared by preparation method
CN112375392A (en) * 2020-11-25 2021-02-19 德阳中碳新材料科技有限公司 Preparation method of graphene heat-conducting interface material
CN112588214A (en) * 2020-12-23 2021-04-02 西北工业大学 Phase-change material microcapsule with photo-thermal conversion and energy storage properties and preparation method thereof
CN113214884A (en) * 2021-04-20 2021-08-06 清华大学 Preparation method of super-regular graphene-based lubricating grease
CN113214884B (en) * 2021-04-20 2022-04-12 清华大学 Preparation method of super-regular graphene-based lubricating grease
WO2022262103A1 (en) * 2021-06-15 2022-12-22 南通大学 Microcapsule having both infrared and radar stealth, preparation method therefor and application thereof
CN113385161A (en) * 2021-07-02 2021-09-14 青岛瑞利特新材料科技有限公司 Formaldehyde removal material of graphene nano composite gel and preparation process
CN113861942A (en) * 2021-09-14 2021-12-31 中北大学 Organic-microcapsule phase change material, preparation method thereof and application thereof in battery thermal management system
CN114181532B (en) * 2021-12-22 2023-01-03 仲恺农业工程学院 Phase-change heat-conducting silicone grease containing macromolecular modifier and preparation method thereof
CN114181532A (en) * 2021-12-22 2022-03-15 仲恺农业工程学院 Phase-change heat-conducting silicone grease containing macromolecular modifier and preparation method thereof
CN114873955A (en) * 2022-04-24 2022-08-09 四川衡鼎建材有限公司 Concrete capable of recycling waste and preparation process thereof
CN114873955B (en) * 2022-04-24 2022-11-08 四川衡鼎建材有限公司 Concrete capable of recycling waste and preparation process thereof
CN115010538B (en) * 2022-05-07 2023-07-04 山西粮缘金土地科技股份有限公司 Double-component composite microorganism water-retention temperature-control slow-release fertilizer and preparation method and application thereof
CN115010538A (en) * 2022-05-07 2022-09-06 山西粮缘金土地科技股份有限公司 Two-component composite microorganism water-retention temperature-control slow-release fertilizer and preparation method and application thereof
CN115073075A (en) * 2022-05-10 2022-09-20 中建西部建设北方有限公司 Super-long structure high-crack-resistance compensation shrinkage concrete and preparation method thereof
CN115073075B (en) * 2022-05-10 2023-02-03 中建西部建设北方有限公司 Super-long structure high-crack-resistance compensation shrinkage concrete and preparation method thereof
CN115043637A (en) * 2022-05-20 2022-09-13 邢台建德水泥有限公司 Cement containing biomass combustion waste material and preparation method thereof
CN114709083B (en) * 2022-05-25 2022-10-25 深圳市今朝时代股份有限公司 Modified graphene composite material and supercapacitor
CN114709083A (en) * 2022-05-25 2022-07-05 深圳市今朝时代股份有限公司 Modified graphene composite material and supercapacitor
CN114989786A (en) * 2022-06-09 2022-09-02 纯钧新材料(深圳)有限公司 Salin resin phase-change microcapsule and preparation method thereof
CN114989786B (en) * 2022-06-09 2023-08-15 纯钧新材料(深圳)有限公司 Sarin resin phase-change microcapsule and preparation method thereof
CN115652464A (en) * 2022-10-10 2023-01-31 南通强生新材料科技股份有限公司 Graphene extremely-cold-resistant gloves and preparation method thereof
CN116019962A (en) * 2022-11-23 2023-04-28 武汉中科先进材料科技有限公司 Antibacterial microcapsule, preparation method thereof, long-acting antibacterial dressing and application
CN116019962B (en) * 2022-11-23 2024-04-16 武汉中科先进材料科技有限公司 Antibacterial microcapsule, preparation method thereof, long-acting antibacterial dressing and application
CN116350727A (en) * 2022-12-27 2023-06-30 北京蜜蜂堂生物医药股份有限公司 Beeswax paste for wax therapy and preparation method thereof
CN116063996B (en) * 2023-04-03 2023-06-20 西南石油大学 Phase-change heat storage microcapsule material suitable for cooling drilling fluid and preparation method thereof
CN116063996A (en) * 2023-04-03 2023-05-05 西南石油大学 Phase-change heat storage microcapsule material suitable for cooling drilling fluid and preparation method thereof
CN117534946A (en) * 2024-01-10 2024-02-09 上海沪正实业有限公司 Nanometer microcapsule heat insulation function master batch and preparation method thereof
CN117534946B (en) * 2024-01-10 2024-04-05 上海沪正实业有限公司 Nanometer microcapsule heat insulation function master batch and preparation method thereof
CN117601456A (en) * 2024-01-22 2024-02-27 四川省宜宾普什建材有限责任公司 Processing technology of large-caliber electric melting type plastic pipe fitting
CN117601456B (en) * 2024-01-22 2024-03-26 四川省宜宾普什建材有限责任公司 Processing technology of large-caliber electric melting type plastic pipe fitting

Also Published As

Publication number Publication date
CN104212416B (en) 2017-04-12
CN104212416A (en) 2014-12-17

Similar Documents

Publication Publication Date Title
WO2016029527A1 (en) Method for preparing paraffin microcapsule phase-change material modified by graphene oxide
CN106367031B (en) A kind of high heat conductance composite phase-change microcapsules and preparation method thereof
CN103289653B (en) High-thermal-conductivity heat-storing nanometer-particle-mixed molten salt and preparation method thereof
CN107384026B (en) A kind of watersoluble plumbago alkene/carbon nanotube compound electro-thermal conversion ink and preparation method
CN104449590A (en) Phase-change energy-storage material nanocapsule and preparation method thereof
CN108774499B (en) Graphene-silicon dioxide composite wall material phase change nanocapsule and preparation method thereof
CN103804614B (en) A kind of preparation method of graphene in-situ modified polyvinyl chloride (PVC) RESINS
CN103752234A (en) Preparation method of oxidized graphene phase change microcapsule
CN105056854A (en) Preparation method for nanometer TiO2 modified composite phase change microcapsule
CN105969317B (en) A kind of Lauxite paraffin microcapsule material and preparation method with the high enthalpy of high heat conductance
CN108300421A (en) A kind of coated by titanium dioxide paraffin microcapsule phase change energy storage material and preparation method thereof
CN109294526B (en) Preparation method of hybrid wall material-coated phase-change submicron capsule based on microemulsion system
CN101967257A (en) Pure acrylic emulsion modified by inorganic nanoparticles and preparation method thereof
CN101544712A (en) Method for preparing phase-transition capsule dispersion liquid through mini-emulsion polymerization
CN106976887A (en) A kind of a large amount of methods for preparing two-dimensional nano mica sheet of utilization liquid phase ultrasound
CN102344700A (en) Preparation method of polystyrene/graphene composite particle
CN108624292B (en) Microcapsule composite phase change energy storage material and preparation method thereof
CN104962242A (en) Low super-cooling degree phase-change material microcapsule and preparation method thereof
CN104744640A (en) Preparation method and application of normal-temperature ketone and hydrazine self-crosslinked nanometer epoxy resin emulsion
CN103359743A (en) Preparation method for monodisperse hollow silicon dioxide nanosphere with controllable size and shell thickness
CN101275051A (en) Acroid resin coating agent and preparation thereof
CN103160178B (en) Preparation method of carbon nanometer-tube modified acrylic resin light-resistant paint
WO2020224080A1 (en) Heat storage and heat transfer material and preparation method therefor
CN109494345A (en) A kind of battery preparation method and battery promoting lithium ion battery safety performance
CN112391148A (en) High-thermal-conductivity and high-enthalpy composite phase change microcapsule and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14900508

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC ( EPO FORM 1205A DATED 20-06-2017 )

122 Ep: pct application non-entry in european phase

Ref document number: 14900508

Country of ref document: EP

Kind code of ref document: A1