TWI764098B - High thermal conductivity and low resistance phase change material microcapsule and its preparation and application - Google Patents
High thermal conductivity and low resistance phase change material microcapsule and its preparation and applicationInfo
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Abstract
Description
本發明有關於一種相變化材料的微膠囊化技術本领域,特別是指一種高導熱低電阻相變化材料微膠囊及其製法和應用。 The invention relates to the technical field of microencapsulation of a phase change material, in particular to a microcapsule of a phase change material with high thermal conductivity and low resistance, and a preparation method and application thereof.
近來由於經濟及生活品質的進步,環境友善能源之需求量大增,因此發展熱能儲存及有效運用熱能之材料備受矚目。相變化材料是適用的材料,因為其可以調節熱量及熱舒適性。此種潛熱儲存型材料較傳統材料有較高的熱儲存密度。其中固-液型相變化材料已被廣泛研發,但其在相變化過程之洩漏問題限制了它的應用。因此經由微膠囊包覆相變化材料可避免其洩漏及與周遭及環境物質之不利反應。然而,一般的微膠囊因為殼層是高分子材料,所以導熱性差且電阻高易產生靜電,導致相變化材料微膠囊的效果並不顯著。 Recently, due to the improvement of economy and quality of life, the demand for environment-friendly energy has greatly increased, so the development of materials for thermal energy storage and effective utilization of thermal energy has attracted much attention. Phase change materials are suitable materials because they can regulate heat and thermal comfort. This latent heat storage material has a higher heat storage density than traditional materials. Among them, solid-liquid phase change materials have been widely developed, but their leakage problems during the phase change process limit their applications. Therefore, encapsulating the phase change material by microcapsules can avoid its leakage and adverse reaction with surrounding and environmental substances. However, because the shell layer of the general microcapsule is a polymer material, the thermal conductivity is poor and the resistance is high, and it is easy to generate static electricity, resulting in the ineffectiveness of the phase change material microcapsule.
為改善上述問題,中華民國發明專利第I535486號公開了一種具導熱殼層相變化微膠囊的製備方法,其係在微膠囊殼層的高分子結構上做改善,利用將原來的壓克力單體(例如:甲基丙烯酸甲酯,Methyl methacrylate,MMA)另外再與矽烷化合物(例如:三乙氧基乙烯基矽烷,Triethoxyvinylsilane)共聚的方法, 進一步讓導熱性材料(如氮化硼)能夠導入殼層材料中,並使用聚乙烯醇(Polyvinyl alcohol,PVA)做為穩定劑,成功製得高導熱之相變化微膠囊。 In order to improve the above-mentioned problems, the Republic of China Invention Patent No. I535486 discloses a preparation method of a phase-change microcapsule with a thermally conductive shell, which is improved on the polymer structure of the microcapsule shell, using the original acrylic sheet. A method of copolymerizing the body (eg: methyl methacrylate, Methyl methacrylate, MMA) with a silane compound (eg: triethoxyvinylsilane, Triethoxyvinylsilane), Furthermore, thermal conductive materials (such as boron nitride) can be introduced into the shell material, and polyvinyl alcohol (PVA) is used as a stabilizer, and phase change microcapsules with high thermal conductivity are successfully prepared.
值得注意的是,前述專利的高導熱微膠囊之電阻較高,若加入非導體材料中(如高分子材料),會有靜電累積之危險。是以,本發明認為有必要提出一種高導熱低電阻相變化材料微膠囊及其製法和應用,以改善上述問題。 It is worth noting that the high thermal conductivity microcapsules of the aforementioned patents have high electrical resistance, and if they are added to non-conductive materials (such as polymer materials), there is a danger of static electricity accumulation. Therefore, the present invention considers that it is necessary to provide a high thermal conductivity and low resistance phase change material microcapsule and its preparation method and application to improve the above problems.
為克服上述技術問題,本發明之目的在於提供高導熱低電阻相變化材料微膠囊及其製法和應用,本發明係採用壓克力單體與矽烷化合物之共聚物做為微膠囊殼層,並另外使用十二烷基硫酸鈉(Sodium dodecyl Sulfate,SDS)做為穩定劑,使得微膠囊尺寸均勻且微小化,並在殼層導入高導熱及低電阻之奈米無機粉體,因此使得微膠囊的表面積增大,且可以快速導熱,達到有效發揮相變化材料之調溫作用。另外,本發明製法製成的高導熱低電阻相變化材料微膠囊在加入非導體材料(如高分子材料)後具有抗靜電效果。承上,本發明製法製成的高導熱低電阻相變化材料微膠囊能夠分別應用在建築材料、高分子複合材料、調溫織物和電子光電產品之散熱或儲能材料等方面。 In order to overcome the above-mentioned technical problems, the purpose of the present invention is to provide microcapsules of phase-change materials with high thermal conductivity and low resistance and their preparation method and application. In addition, sodium dodecyl sulfate (SDS) is used as a stabilizer to make the size of the microcapsules uniform and miniaturized, and nano-inorganic powders with high thermal conductivity and low resistance are introduced into the shell layer, so that the microcapsules are The surface area of the material is increased, and it can conduct heat quickly, so as to effectively exert the temperature regulation effect of the phase change material. In addition, the high thermal conductivity and low resistance phase change material microcapsules prepared by the method of the present invention have antistatic effect after adding non-conductive materials (such as polymer materials). In conclusion, the high thermal conductivity and low resistance phase change material microcapsules prepared by the method of the present invention can be respectively applied in building materials, polymer composite materials, temperature regulating fabrics and heat dissipation or energy storage materials of electronic and optoelectronic products.
緣是,為達上述目的,本發明所提供一種高導熱低電阻相變化材料微膠囊之製法,其步驟包括:(A)將壓克力單體與矽烷化合物共聚,並加入起始劑,於油浴加熱攪拌進行預聚合反應,形成第一溶液;(B)提供一相變化材料; (C)將穩定劑十二烷基硫酸鈉水溶液加入該相變化材料,並升溫超過該相變化材料的熔點,以進行液化動作,並攪拌均勻,形成第二溶液;(D)將該第二溶液加入該第一溶液,並攪拌均勻;(E)加入乙二醇二甲基丙烯酸酯及高熱傳導低電阻之奈米無機粉體,再加入起始劑,以攪拌油浴加熱完成微膠囊聚合包覆;(F)經冰浴、離心、過濾,取下層微膠囊烘乾,得到導熱殼層相變化材料微膠囊。 The reason is that, in order to achieve the above purpose, the present invention provides a method for preparing microcapsules of phase change materials with high thermal conductivity and low resistance. The oil bath is heated and stirred to carry out the prepolymerization reaction to form the first solution; (B) provide a phase change material; (C) adding the stabilizer sodium dodecyl sulfate aqueous solution to the phase change material, and raising the temperature to exceed the melting point of the phase change material to perform a liquefaction action, and stirring evenly to form a second solution; (D) the second solution The solution is added to the first solution and stirred evenly; (E) ethylene glycol dimethacrylate and nano-inorganic powder with high thermal conductivity and low resistance are added, and then an initiator is added, and the microcapsule polymerization is completed by heating in a stirring oil bath Coating; (F) ice bath, centrifugation, filtration, and drying of the lower layer of microcapsules to obtain thermally conductive shell phase change material microcapsules.
本發明相變化材料微膠囊的製法中,該高熱傳導低電阻之奈米無機粉體係選自石墨、石墨烯或碳管中的一種或其中兩種以上之組合。 In the preparation method of the phase change material microcapsule of the present invention, the nano-inorganic powder system with high thermal conductivity and low resistance is selected from one or a combination of two or more of graphite, graphene or carbon tube.
本發明相變化材料微膠囊的製法中,步驟(A)的油浴加熱溫度範圍為50℃~120℃。 In the preparation method of the phase change material microcapsules of the present invention, the heating temperature of the oil bath in step (A) ranges from 50°C to 120°C.
本發明相變化材料微膠囊的製法中,步驟(C)的升溫溫度範圍為30℃~80℃。 In the preparation method of the phase change material microcapsules of the present invention, the temperature range of the temperature increase in step (C) is 30°C to 80°C.
本發明相變化材料微膠囊的製法中,步驟(E)的油浴加熱溫度範圍為50℃~120℃。 In the preparation method of the phase change material microcapsules of the present invention, the oil bath heating temperature in step (E) ranges from 50°C to 120°C.
本發明相變化材料微膠囊的製法中,該壓克力單體係選自丙烯酸甲酯、甲基丙烯酸甲酯、或甲基丙烯酸羥乙酯。 In the preparation method of the phase change material microcapsules of the present invention, the acrylic monomer system is selected from methyl acrylate, methyl methacrylate, or hydroxyethyl methacrylate.
本發明相變化材料微膠囊的製法中,該矽烷化合物係選自三甲氧基乙烯矽烷(trimethoxyvinylsilane)或三乙氧基乙烯矽烷(triethoxyvinyl silane)。 In the preparation method of the phase change material microcapsules of the present invention, the silane compound is selected from trimethoxyvinylsilane or triethoxyvinyl silane.
本發明相變化材料微膠囊的製法中,該起始劑係為過氧化苯甲醯。 In the preparation method of the phase change material microcapsules of the present invention, the starting agent is benzyl peroxide.
本發明相變化材料微膠囊的製法中,該相變化材料係有機相變化材料,該有機相變化材料係選自於高級脂肪烴、高級脂肪酸、高級脂肪酸酯、高級脂肪酸的鹽、高級脂肪醇、芳香烴、芳香酮、芳香醯胺中的一種或其中兩種以上之混合物所組成之群組。 In the preparation method of the phase change material microcapsules of the present invention, the phase change material is an organic phase change material, and the organic phase change material is selected from the group consisting of higher aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, salts of higher fatty acids, and higher aliphatic alcohols , aromatic hydrocarbons, aromatic ketones, aromatic amides, or a group consisting of a mixture of two or more of them.
本發明相變化材料微膠囊的製法中,該壓克力單體與該矽烷化合物之當量比為5:1。 In the preparation method of the phase change material microcapsule of the present invention, the equivalent ratio of the acrylic monomer and the silane compound is 5:1.
本發明相變化材料微膠囊的製法中,該相變化材料微膠囊係為一核殼材料,其中核材係為有機相變化材料,殼材係為矽烷化合物與壓克力單體之共聚物。 In the preparation method of the phase change material microcapsule of the present invention, the phase change material microcapsule is a core-shell material, wherein the core material is an organic phase change material, and the shell material is a copolymer of a silane compound and an acrylic monomer.
本發明相變化材料微膠囊的製法中,該相變化材料之添加比例係佔該微膠囊整體的20wt%~60wt%。 In the preparation method of the phase change material microcapsule of the present invention, the addition ratio of the phase change material is 20wt%-60wt% of the whole microcapsule.
本發明相變化材料微膠囊的製法中,該高熱傳導及低電阻奈米無機粉體之添加比例係佔該微膠囊整體的10wt%~40wt%。 In the preparation method of the phase change material microcapsule of the present invention, the addition ratio of the high thermal conductivity and low resistance nano-inorganic powder accounts for 10wt% to 40wt% of the whole microcapsule.
本發明相變化材料微膠囊的製法中,該攪拌所使用機器為用磁攪拌機、馬達式攪拌器或均質機。 In the preparation method of the phase change material microcapsules of the present invention, the machine used for the stirring is a magnetic stirrer, a motor stirrer or a homogenizer.
本發明另提供一種高導熱低電阻相變化材料微膠囊,其係以如前所述之高導熱低電阻相變化材料微膠囊之製法製成,該微膠囊之尺寸小於等於200奈米。 The present invention further provides a phase change material microcapsule with high thermal conductivity and low resistance.
本發明另提供一種高導熱低電阻相變化材料微膠囊的應用,其係以如前所述之高導熱低電阻相變化材料微膠囊之製法製成,其中,該微膠囊用於添加在高分子材料中形成調溫複合材料,該調溫複合材料的導熱係數為0.4~0.6W/mK,該調溫複合材料的電阻為2×105~2×106Ω/sq。 The present invention further provides the application of a phase change material microcapsule with high thermal conductivity and low resistance. A temperature-adjusting composite material is formed in the material, the thermal conductivity of the temperature-adjusting composite material is 0.4-0.6 W/mK, and the resistance of the temperature-adjusting composite material is 2×10 5 -2×10 6 Ω/sq.
本發明通過前述製法製得之高導熱低電阻相變化材料微膠囊可加入建築或高分子複合材料中以調節溫度及降低空調用量;亦可加入紡織材料中調節織品溫度,以增進使用之舒適性降低空調用量;或做為電子光電產品之散熱或儲能材料。此外,近年來由於極端氣候及電能短缺,使得節能相關產品之市場逐年成長,而相變化材料微膠囊因為具備恆溫作用,且可防止相變化洩漏,且具備節能儲熱及使用安全之功能,因此預期市場接受度高。更進一步地,本發明之相變化材料微膠囊具備高導熱低電阻之特性,其高導熱特性可以使熱能傳遞加速,而低電阻可以解決材料靜電累積之問題,確實達到抗靜電效果。 The high thermal conductivity and low resistance phase change material microcapsules of the present invention obtained by the above-mentioned preparation method can be added to building or polymer composite materials to adjust the temperature and reduce the amount of air conditioners; they can also be added to textile materials to adjust the temperature of fabrics to improve the comfort of use. Reduce the amount of air conditioners; or as a heat dissipation or energy storage material for electronic optoelectronic products. In addition, in recent years, due to extreme climate and power shortage, the market for energy-saving related products has grown year by year. The phase change material microcapsules have a constant temperature effect, can prevent phase change leakage, and have the functions of energy-saving heat storage and safe use. High market acceptance is expected. Furthermore, the phase change material microcapsules of the present invention have the characteristics of high thermal conductivity and low resistance, and the high thermal conductivity can accelerate the transfer of heat energy, and the low resistance can solve the problem of static electricity accumulation in the material, and indeed achieve the antistatic effect.
有關於本發明為達成上述目的,所採用之技術、手段及其他功效,茲舉一較佳可行實施例並配合圖式詳細說明如後。 Regarding the techniques, means and other effects adopted by the present invention to achieve the above-mentioned objects, a preferred feasible embodiment is given and described in detail with the drawings as follows.
A~F:高導熱低電阻相變化材料微膠囊之製法之步驟 A~F: The steps of making microcapsules of phase change materials with high thermal conductivity and low resistance
10:盒體 10: Box body
20:遮光屏障 20: Blackout Barrier
30:溫度感測裝置 30: Temperature sensing device
40:光源 40: Light source
圖1是本發明高導熱低電阻相變化材料微膠囊之製法的流程示意圖。 FIG. 1 is a schematic flow chart of a method for preparing microcapsules of phase-change materials with high thermal conductivity and low resistance according to the present invention.
圖2是以PVA為穩定劑所製備之微膠囊的放大結構圖。 Figure 2 is an enlarged structural view of the microcapsules prepared with PVA as a stabilizer.
圖3是以SDS為穩定劑所製備之微膠囊的放大結構圖。 Figure 3 is an enlarged structural view of the microcapsules prepared with SDS as a stabilizer.
圖4是本發明將高密度聚乙烯盒或微膠囊/高密度聚乙烯盒進行相變溫度試驗的裝置示意圖。 FIG. 4 is a schematic diagram of a device for conducting a phase transition temperature test on a high-density polyethylene box or a microcapsule/high-density polyethylene box according to the present invention.
為利於對本發明的瞭解,以下結合實施例進行說明。 In order to facilitate the understanding of the present invention, the following description is given in conjunction with the embodiments.
本發明特徵與優點的一些實施例將在以下說明中詳細敘述。應理解的是本發明能夠在不同的態樣上具有各種的變化,然其皆不脫離本發明的範圍,且其中的說明及圖式在本質上係當作說明之用,而非用於限制本發明。 Some embodiments of the features and advantages of the present invention are set forth in detail in the following description. It should be understood that the present invention can have various changes in different aspects without departing from the scope of the present invention, and the descriptions and drawings therein are essentially used for illustration rather than limitation this invention.
本發明之高導熱低電阻相變化材料微膠囊之製法首先將壓克力單體改質,然後添加奈米導熱材使其接合至改質壓克力單體,最後製備成導熱殼層相變化材料微膠囊,描述如下: The manufacturing method of the high thermal conductivity and low resistance phase change material microcapsules of the present invention firstly modifies the acrylic monomer, then adds the nano thermal conductive material to bond it to the modified acrylic monomer, and finally prepares the phase change of the thermally conductive shell layer Materials Microcapsules, described below:
一、壓克力單體之改質: 1. Modification of acrylic monomer:
以矽烷化合物(vinylsilane,VS)及壓克力單體(acrylic monomer,AM)為反應單體,在不使用有機溶劑環境下經由過氧化物起始反應聚合而成共聚合物(VS-AM copolymer),反應式如下式(1)。其中矽烷化合物採用三甲氧基乙烯矽烷(trimethoxyvinylsilane)、或三乙氧基乙烯矽烷(triethoxyvinyl silane)。壓克力單體為丙烯酸甲酯、甲基丙烯酸甲酯、或甲基丙烯酸羥乙酯。 Using vinylsilane (VS) and acrylic monomer (AM) as reactive monomers, the copolymer (VS-AM copolymer) is polymerized through peroxide initiation reaction without the use of organic solvents. ), the reaction formula is as follows (1). The silane compound is trimethoxyvinylsilane or triethoxyvinylsilane. The acrylic monomer is methyl acrylate, methyl methacrylate, or hydroxyethyl methacrylate.
二、添加奈米導熱材使其接合至改質壓克力單體上: 2. Add nano thermal conductive material to bond it to the modified acrylic monomer:
在有機材料中,加入具有高熱傳導性質的奈米無機粉體,該奈米無機粉體係選自石墨、石墨烯或碳管中的一種或其中兩種以上之組合,能賦予有機材料有效提升熱傳導性,製備成高導熱複合材料。而本發明所合成之矽烷化合物-壓克力共聚合物(VS-MMA copolymer)與奈米導熱材可形成如下式(2)的化 學鍵結,可有效增進高熱傳導性質的無機粉體與有機基材之相容性,該高熱傳導性質的奈米無機粉體較佳的添加比率為佔該微膠囊整體的10wt%~40wt%。 In the organic material, adding a nano-inorganic powder with high thermal conductivity properties, the nano-inorganic powder system is selected from one or a combination of two or more of graphite, graphene or carbon tube, which can effectively improve the thermal conductivity of the organic material. , and prepared into a high thermal conductivity composite material. The silane compound-acrylic copolymer (VS-MMA copolymer) and the nano thermal conductive material synthesized in the present invention can form the compound of the following formula (2) It can effectively improve the compatibility between the inorganic powder with high thermal conductivity and the organic substrate. The preferred addition ratio of the nano-inorganic powder with high thermal conductivity is 10wt%~40wt% of the whole microcapsule .
三、導熱殼層相變化材料微膠囊之製備: 3. Preparation of thermal conductive shell phase change material microcapsules:
導熱殼層相變化材料微膠囊,係以相變化材料為核、共聚高分子為殼,其製備方法如下:將壓克力單體及矽烷化合物攪拌混合,然後加入微量起始劑。將加入微量起始劑後的壓克力單體及矽烷化合物混合物,於油浴加熱下攪拌進行預聚合,形成第一溶液。將相變化材料加入十二烷基硫酸鈉(SDS)水溶液,並升溫超過相變化材料的熔點,以進行液化動作,形成第二溶液。將第一溶液第二溶液混合,並加入乙二醇二甲基丙烯酸酯及導熱材料,攪拌後形成導熱殼層相變化材料微膠囊溶液。然後冰浴、離心、過濾後、取下層微膠囊烘乾,即得到導熱殼層相變化材料微膠囊。 The thermally conductive shell phase change material microcapsule is based on the phase change material as the core and the copolymerized polymer as the shell. The mixture of acrylic monomer and silane compound after adding a small amount of initiator is stirred under oil bath heating to carry out prepolymerization to form a first solution. The phase change material is added to an aqueous solution of sodium dodecyl sulfate (SDS), and the temperature is raised beyond the melting point of the phase change material to perform a liquefaction action to form a second solution. The first solution and the second solution are mixed, and ethylene glycol dimethacrylate and a thermally conductive material are added, and after stirring, a thermally conductive shell phase change material microcapsule solution is formed. Then, after ice bathing, centrifugation and filtration, the microcapsules of the lower layer are taken out and dried to obtain the microcapsules of the thermally conductive shell phase change material.
其中,本發明所述之相變化材料為有機相變化材料;該有機相變化材料主要為高級脂肪烴、高級脂肪酸、高級脂肪酸酯、高級脂肪酸的鹽、高級脂肪醇、芳香烴、芳香酮、芳香醯胺、及其混合物所構成之群組,但不限於上述之有機相變化材料,該相變化材料添加的比率較佳為佔該微膠囊整體的20wt%~60wt%。 Wherein, the phase change material described in the present invention is an organic phase change material; the organic phase change material is mainly higher aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, salts of higher fatty acids, higher aliphatic alcohols, aromatic hydrocarbons, aromatic ketones, The group consisting of aromatic amides and mixtures thereof, but not limited to the above organic phase change material, the phase change material is preferably added in a ratio of 20wt% to 60wt% of the entire microcapsule.
高級脂肪烴通常是含6個以上碳原子的脂肪烴,較佳為6~36個碳原子;高級脂肪醇通常是含6個以上碳原子的脂肪烴,較佳為6~36個碳原子。 Higher aliphatic hydrocarbons are usually aliphatic hydrocarbons containing more than 6 carbon atoms, preferably 6-36 carbon atoms; higher aliphatic alcohols are usually aliphatic hydrocarbons containing more than 6 carbon atoms, preferably 6-36 carbon atoms.
如圖1所示,顯示本發明高導熱低電阻相變化材料微膠囊之製法具體實施步驟流程,本發明製法的步驟包括: As shown in Figure 1, the specific implementation steps of the method for preparing the high thermal conductivity and low resistance phase change material microcapsules of the present invention are shown, and the steps of the method of the present invention include:
(A)將壓克力單體與矽烷化合物共聚,並加入起始劑,於油浴加熱攪拌進行預聚合反應,形成第一溶液。於本發明實施例中,步驟(A)的油浴加熱溫度範圍較佳為50℃~120℃;該壓克力單體係選自丙烯酸甲酯、甲基丙烯酸甲酯、或甲基丙烯酸羥乙酯;該矽烷化合物係選自三甲氧基乙烯矽烷(trimethoxyvinylsilane)或三乙氧基乙烯矽烷(triethoxyvinyl silane);該起始劑係為過氧化苯甲醯。其中,該壓克力單體與該矽烷化合物之當量比為5:1。 (A) Copolymerize the acrylic monomer and the silane compound, add an initiator, heat and stir in an oil bath to carry out a prepolymerization reaction to form a first solution. In the embodiment of the present invention, the heating temperature range of the oil bath in step (A) is preferably 50°C to 120°C; the acrylic monomer system is selected from methyl acrylate, methyl methacrylate, or hydroxy methacrylate. Ethyl ester; the silane compound is selected from trimethoxyvinylsilane or triethoxyvinyl silane; the initiator is benzyl peroxide. Wherein, the equivalent ratio of the acrylic monomer and the silane compound is 5:1.
(B)提供一相變化材料。於本發明實施例中,該相變化材料係有機相變化材料,該有機相變化材料係選自於高級脂肪烴、高級脂肪酸、高級脂肪酸酯、高級脂肪酸的鹽、高級脂肪醇、芳香烴、芳香酮、芳香醯胺中的一種或其中兩種以上之混合物所組成之群組。其中,該相變化材料之添加比例係佔該微膠囊整體的20wt%~60wt%。 (B) Provides a phase change material. In the embodiment of the present invention, the phase change material is an organic phase change material, and the organic phase change material is selected from higher aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, salts of higher fatty acids, higher aliphatic alcohols, aromatic hydrocarbons, A group consisting of one of aromatic ketones and aromatic amides or a mixture of two or more of them. Wherein, the addition ratio of the phase change material accounts for 20wt% to 60wt% of the whole microcapsule.
(C)將穩定劑十二烷基硫酸鈉水溶液加入該相變化材料,並升溫超過該相變化材料的熔點,以進行液化動作,並攪拌均勻,形成第二溶液;於本發明實施例中,步驟(C)的升溫溫度範圍較佳為30℃~80℃。 (C) adding the stabilizer sodium dodecyl sulfate aqueous solution to the phase change material, and heating up to exceed the melting point of the phase change material, to carry out liquefaction action, and stirring uniformly to form the second solution; In the embodiment of the present invention, The temperature range of the temperature increase in step (C) is preferably 30°C to 80°C.
(D)將該第二溶液加入該第一溶液,並攪拌均勻; (D) this second solution is added to this first solution, and stir;
(E)加入乙二醇二甲基丙烯酸酯及高熱傳導低電阻之奈米無機粉體,再加入起始劑,以攪拌油浴加熱完成微膠囊聚合包覆;於本發明實施例中,該高熱傳導低電阻之奈米無機粉體係選自石墨、石墨烯或碳管中的一種或其中兩 種以上之組合。於本發明實施例中,步驟(E)的油浴加熱溫度範圍較佳為50℃~120℃;該起始劑係為過氧化苯甲醯。其中,該高熱傳導及低電阻奈米無機粉體之添加比例係佔該微膠囊整體的10wt%~40wt%。 (E) adding ethylene glycol dimethacrylate and nano-inorganic powder with high thermal conductivity and low resistance, then adding an initiator, and heating in a stirred oil bath to complete the polymerization and coating of microcapsules; in the embodiment of the present invention, the The nano-inorganic powder system with high thermal conductivity and low resistance is selected from one or two of graphite, graphene or carbon tube. a combination of more than one. In the embodiment of the present invention, the heating temperature range of the oil bath in step (E) is preferably 50°C to 120°C; the starting agent is benzyl peroxide. Wherein, the addition ratio of the high thermal conductivity and low resistance nano-inorganic powder accounts for 10wt% to 40wt% of the whole microcapsule.
(F)經冰浴、離心、過濾,取下層微膠囊烘乾,得到導熱殼層相變化材料微膠囊。 (F) After ice bath, centrifugation and filtration, the microcapsules of the lower layer are taken out and dried to obtain the microcapsules of the phase change material of the thermally conductive shell layer.
於本發明實施例中,製法步驟中提及的攪拌較佳採用機器進行,該機器可選自磁攪拌機、馬達式攪拌器或均質機,但不限於此。 In the embodiment of the present invention, the stirring mentioned in the steps of the preparation method is preferably performed by a machine, and the machine can be selected from a magnetic stirrer, a motor stirrer or a homogenizer, but is not limited thereto.
以下提供本發明製法實施例一至實施例四: The following provides method of the present invention embodiment one to embodiment four:
實施例一: Example 1:
實施例一係將甲基丙烯酸甲酯加入過氧化苯甲醯於油浴加熱下聚合成預聚物溶液。另將與甲基丙烯酸甲酯重量比例1:1之石蠟(有機相變材料)加入十二烷基硫酸鈉(Sodium dodecyl Sulfate,SDS)水溶液中,並升溫超過石蠟的熔點,攪拌均勻。倒入預聚物溶液,並攪拌均勻。加入乙二醇二甲基丙烯酸酯,置於油浴加熱下以攪拌均勻。經冰浴、離心、過濾程序、取上層微膠囊烘乾,得相變化微膠囊。測得此微膠囊之熱傳導係數為0.1996W/mk。電阻為>1016Ω/sq。 Example 1 is to add methyl methacrylate to benzyl peroxide and polymerize it into a prepolymer solution under the heating of an oil bath. In addition, paraffin (organic phase change material) in a weight ratio of 1:1 with methyl methacrylate was added to an aqueous solution of sodium dodecyl sulfate (SDS), and the temperature was raised above the melting point of the paraffin, and stirred evenly. Pour in the prepolymer solution and stir well. Add ethylene glycol dimethacrylate and heat in an oil bath to stir well. After ice bath, centrifugation, filtration procedures, and drying of the upper microcapsules, phase change microcapsules were obtained. The thermal conductivity of the microcapsules was measured to be 0.1996 W/mk. Resistance is >10 16 Ω/sq.
實施例二: Embodiment 2:
實施例二係將甲基丙烯酸甲酯及矽烷化合物三甲氧基乙烯矽烷(trimethoxyvinylsilane)以當量比5:1於60℃油浴加熱下混合。加入過氧化苯甲醯於油浴加熱下聚合成預聚物溶液。另將與甲基丙烯酸甲酯重量比例3:1之石蠟(有機相變材料)加入十二烷基硫酸鈉水溶液中,並升溫超過石蠟的熔點,攪拌均勻。倒入預聚物溶液,並攪拌均勻。加入乙二醇二甲基丙烯酸酯,置於油浴加熱下攪拌均勻。 冰浴、離心、過濾、取上層微膠囊烘乾,得相變化微膠囊。測得此微膠囊之熱傳導係數為0.1985W/mk。電阻為>1016Ω/sq。 In the second embodiment, methyl methacrylate and the silane compound trimethoxyvinylsilane were mixed in an equivalent ratio of 5:1 under heating in an oil bath at 60°C. Add benzyl peroxide and polymerize into a prepolymer solution under heating in an oil bath. In addition, paraffin wax (organic phase change material) in a weight ratio of 3:1 with methyl methacrylate was added to the sodium dodecyl sulfate aqueous solution, and the temperature was raised to exceed the melting point of the paraffin wax, and stirred evenly. Pour in the prepolymer solution and stir well. Add ethylene glycol dimethacrylate, and stir evenly under heating in an oil bath. Ice bath, centrifugation, filtration, and drying of the upper microcapsules to obtain phase change microcapsules. The thermal conductivity of the microcapsules was measured to be 0.1985 W/mk. Resistance is >10 16 Ω/sq.
實施例三: Embodiment three:
實施例三係將甲基丙烯酸甲酯及矽烷化合物三甲氧基乙烯矽烷(triethoxyvinylsilane)以當量比5:1於60℃油浴加熱下混合。加入過氧化苯甲醯於油浴加熱下聚合成預聚物溶液。另將與甲基丙烯酸甲酯重量比例1:1之石蠟(有機相變材料)加入十二烷基硫酸鈉水溶液中,並升溫超過石蠟的熔點,攪拌均勻。倒入預聚物溶液,並攪拌均勻。加入乙二醇二甲基丙烯酸酯及奈米石墨,置於油浴加熱下攪拌均勻,其中奈米石墨添加比例為與甲基丙烯酸甲酯重量比例1:2。冰浴、離心、過濾、取下層微膠囊烘乾,製得本發明之高導熱低電阻相變化材料微膠囊。測得此微膠囊之熱傳導係數為1.136W/mk。電阻為1.831×103Ω/sq。 In the third embodiment, methyl methacrylate and the silane compound triethoxyvinylsilane were mixed at an equivalent ratio of 5:1 under heating in an oil bath at 60°C. Add benzyl peroxide and polymerize into a prepolymer solution under heating in an oil bath. In addition, paraffin (organic phase change material) in a weight ratio of 1:1 with methyl methacrylate was added to the sodium dodecyl sulfate aqueous solution, and the temperature was raised to exceed the melting point of the paraffin, and stirred evenly. Pour in the prepolymer solution and stir well. Add ethylene glycol dimethacrylate and nano-graphite, place it under heating in an oil bath and stir evenly, wherein the ratio of nano-graphite to methyl methacrylate is 1:2 by weight. Ice bath, centrifugation, filtration, and drying of the microcapsules in the lower layer to obtain the microcapsules of the phase change material with high thermal conductivity and low resistance of the present invention. The thermal conductivity of the microcapsules was measured to be 1.136 W/mk. The resistance was 1.831×10 3 Ω/sq.
實施例四: Embodiment 4:
實施例四係將甲基丙烯酸甲酯及矽烷化合物三甲氧基乙烯矽烷(triethoxyvinylsilane)以當量比5:1於60℃油浴加熱下混合。加入過氧化苯甲醯於油浴加熱下聚合成預聚物溶液。另將與甲基丙烯酸甲酯重量比例3:1之石蠟(有機相變材料)加入十二烷基硫酸鈉水溶液中,並升溫超過石蠟的熔點,攪拌均勻。倒入預聚物溶液,並攪拌均勻。加入乙二醇二甲基丙烯酸酯及奈米石墨,置於油浴加熱下攪拌均勻,其中奈米石墨添加比例為與甲基丙烯酸甲酯重量比例1:2。冰浴、離心、過濾、取下層微膠囊烘乾,製得本發明之高導熱低電阻相變化材料微膠囊。測得此微膠囊之熱傳導係數為1.144W/mk。電阻為1.712×103Ω/sq。 In the fourth example, methyl methacrylate and the silane compound triethoxyvinylsilane were mixed at an equivalent ratio of 5:1 under heating in an oil bath at 60°C. Add benzyl peroxide and polymerize into a prepolymer solution under heating in an oil bath. In addition, paraffin wax (organic phase change material) in a weight ratio of 3:1 with methyl methacrylate was added to the sodium dodecyl sulfate aqueous solution, and the temperature was raised to exceed the melting point of the paraffin wax, and stirred evenly. Pour in the prepolymer solution and stir well. Add ethylene glycol dimethacrylate and nano-graphite, place it under heating in an oil bath and stir evenly, wherein the ratio of nano-graphite to methyl methacrylate is 1:2 by weight. Ice bath, centrifugation, filtration, and drying of the microcapsules in the lower layer to obtain the microcapsules of the phase change material with high thermal conductivity and low resistance of the present invention. The thermal conductivity of the microcapsules was measured to be 1.144 W/mk. The resistance was 1.712×10 3 Ω/sq.
藉此,本發明通過前述製法實施例製得之高導熱低電阻相變化材料微膠囊,如圖3所示,其尺寸可達200奈米以下,並有良好之均勻性,而習知以
PVA為穩定劑之膠囊尺寸則如圖2所示大至2微米且較不均勻。本發明之高導熱低電阻相變化材料微膠囊可用於加入高分子材料中形成調溫複合材料,該調溫複合材料的導熱係數可達0.6W/mK,並可使高分子材料的電阻從7.96×1015Ω/sq降低到調溫複合材料的2.17×105Ω/sq,從而確實形成抗靜電之功能。另外,如圖4所示,顯示將習知高密度聚乙烯及本發明微膠囊/高密度聚乙烯分別製成盒體10後進行相變溫度試驗的裝置示意圖,其包括將高密度聚乙烯盒體或微膠囊/高密度聚乙烯盒體分別設置於遮光屏障20內部並連接溫度感測裝置30後,令光源40由上向下照光以測量相變溫度變化。配合參閱表1的溫度分析數據,可以發現照光3小時後微膠囊/高密度聚乙烯盒之表面及盒內溫度為39.6℃、36.5℃,相較於高密度聚乙烯盒溫度為45.8℃、40.5℃,明顯下降4~6℃。且微膠囊/高密度聚乙烯盒之溫度在照光1小時以後就幾乎維持在36.5℃,證實加入相變化材料微膠囊確實具有調節溫度之特性,並使室內溫度下降。
Thereby, the microcapsules of the phase change material with high thermal conductivity and low resistance prepared by the above-mentioned preparation method of the present invention, as shown in FIG. 3 , have a size of less than 200 nanometers, and have good uniformity. The size of the capsules, which are stabilizers, is as large as 2 microns as shown in Figure 2 and is less uniform. The high thermal conductivity and low resistance phase change material microcapsules of the present invention can be used to form a temperature-adjusting composite material by adding it into a polymer material. ×10 15 Ω/sq is reduced to 2.17×10 5 Ω/sq of the temperature-adjusting composite material, so that the antistatic function is indeed formed. In addition, as shown in FIG. 4 , a schematic diagram of a device for conducting a phase transition temperature test after the conventional high-density polyethylene and the microcapsules/high-density polyethylene of the present invention are respectively made into
A~F:高導熱低電阻相變化材料微膠囊之製法之步驟A~F: The steps of making microcapsules of phase change materials with high thermal conductivity and low resistance
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