JP2016101536A - Method of manufacturing phase change microcapsule having heat transfer skeleton layer - Google Patents
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 97
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012782 phase change material Substances 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims description 78
- 238000010438 heat treatment Methods 0.000 claims description 48
- 239000003921 oil Substances 0.000 claims description 40
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- 239000012074 organic phase Substances 0.000 claims description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 18
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 18
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 15
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 15
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000011162 core material Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052582 BN Inorganic materials 0.000 claims description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- -1 fatty acid ester Chemical class 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 150000008430 aromatic amides Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000008365 aromatic ketones Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002775 capsule Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- 229920000620 organic polymer Polymers 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 48
- 239000012188 paraffin wax Substances 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
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Abstract
Description
本発明は相変化マイクロカプセルの膜材中にナノ伝熱材料を加える製造方法に関し、特に、相変化マイクロカプセルの膜材中に高伝熱性のナノ伝熱材料を加える製造方法に関する。まずビニルシランとアクリルモノマーを採用した重合で共重合体を生成した後、無機伝熱材料を加え、相変化材料を芯とし、伝熱材料を含む共重合体を骨格とした相変化マイクロカプセルを製造して、これにより伝熱骨格層を備えた相変化マイクロカプセルの製造という目的を達する。 The present invention relates to a manufacturing method of adding a nano heat transfer material into a film material of phase change microcapsules, and more particularly to a manufacturing method of adding a highly heat transfer nano heat transfer material into a film material of phase change microcapsules. First, a copolymer is produced by polymerization using vinyl silane and acrylic monomer, and then an inorganic heat transfer material is added to produce phase change microcapsules with the phase change material as the core and the copolymer containing the heat transfer material as the skeleton. Thus, the objective of producing phase change microcapsules with a heat transfer skeleton layer is achieved.
既知の通り、相変化材料（Ｐｈａｓｅ ｃｈａｎｇｅ ｍａｔｅｒｉａｌｓ、ＰＣＭ）は固相から液相に、または液相から固相に変化可能な物質であり、かつ相変化の発生時に大量の潜熱の吸収または放出を伴い、相変化材料の最大の特徴は、それが大量の潜熱を吸収または放出するとき、システムの温度を変化なく、または小さい変化範囲で維持できることにある。一般に相変化材料を応用するときは、その相変化時により多くの熱を吸収または放出できる潜熱値が比較的大きい相変化材料を選択することで、よりよい効果が得られる。しかし、相変化材料を直接応用すると、相変化の過程で溶融のために材料の漏洩及び損失が発生し、材料の使用寿命が短縮される。マイクロカプセルは微量の物質を骨格層とする方式で別の材料の表面を包み込む技術であり、マイクロカプセル技術を利用することで、相変化材料の溶融時に生じる体積変化と材料漏洩の問題を回避することができる。このほか、マイクロカプセル化後の材料は粒径が小さく、比表面積が大きいため、より大きな伝熱面積を提供する。 As is known, phase change materials (PCM) are substances that can change from the solid phase to the liquid phase, or from the liquid phase to the solid phase, and absorb or release a large amount of latent heat when the phase change occurs. Accordingly, the greatest feature of a phase change material is that when it absorbs or releases a large amount of latent heat, the temperature of the system can be kept unchanged or in a small range of change. In general, when a phase change material is applied, a better effect can be obtained by selecting a phase change material having a relatively large latent heat value that can absorb or release more heat during the phase change. However, if the phase change material is applied directly, leakage and loss of the material occur due to melting in the process of phase change, and the service life of the material is shortened. Microcapsule is a technology that envelops the surface of another material by using a small amount of substance as a skeletal layer. By using microcapsule technology, the problem of volume change and material leakage that occurs when the phase change material melts is avoided. be able to. In addition, since the material after microencapsulation has a small particle size and a large specific surface area, it provides a larger heat transfer area.
しかしながら、マイクロカプセル膜材は多くが有機高分子材料であり、その熱伝達係数が非常に低いため、膜材は相変化材料の漏洩を防止することはできるものの、熱の伝達速度を低下させてしまう。 However, many of the microcapsule membrane materials are organic polymer materials, and their heat transfer coefficient is very low, so the membrane materials can prevent the leakage of phase change materials, but reduce the heat transfer rate. End up.
従来のマイクロカプセル膜材の熱伝達係数が非常に低く、熱の伝達速度が低下する問題を解決するため、本発明の目的は、伝熱骨格層を備えた相変化マイクロカプセルの製造方法を提供することにある。 In order to solve the problem that the heat transfer coefficient of the conventional microcapsule membrane material is very low and the heat transfer rate is lowered, an object of the present invention is to provide a method of manufacturing a phase change microcapsule having a heat transfer skeleton layer There is to do.
上述の目的及びその他の目的を達するため、本発明の伝熱骨格層を備えた相変化マイクロカプセルの製造方法は、膜材中にナノ伝熱材料を加えることでその熱伝達係数を高め、相変化材料の熱の放出または吸収を加速し、効果的な伝熱、放熱、エネルギー貯蔵等の効果を達するとともに、まずビニルシランとアクリルモノマーを重合して共重合体を生成した後、ナノ伝熱材を加えると、ナノ伝熱材表面の極性官能基がビニルシランと縮合して化学結合を形成するため、ナノ伝熱材料と共重合体の相容性が大幅に向上され、同時にマイクロカプセルで相変化複合材料を被覆する二段階プロセス（塊状重合と乳化重合）でナノ伝熱材料を安定的に分散させることができ、伝熱骨格層を備えた相変化マイクロカプセルを製造することができる。 In order to achieve the above-mentioned object and other objects, the method of manufacturing a phase change microcapsule having the heat transfer skeleton layer of the present invention increases the heat transfer coefficient by adding a nano heat transfer material in the film material, Accelerates the release or absorption of heat from the change material, achieves effective heat transfer, heat dissipation, energy storage, etc., and first forms a copolymer by polymerizing vinyl silane and acrylic monomer, then nano heat transfer material Is added, the polar functional group on the surface of the nano heat transfer material is condensed with vinyl silane to form a chemical bond, which greatly improves the compatibility of the nano heat transfer material and the copolymer, and at the same time changes the phase in the microcapsule. The nano heat transfer material can be stably dispersed by a two-step process (bulk polymerization and emulsion polymerization) for coating the composite material, and phase change microcapsules having a heat transfer skeleton layer can be manufactured.
本発明の製造の流れは次の通りである。 The manufacturing flow of the present invention is as follows.
一、アクリルモノマーの改質
ビニルシラン（ｖｉｎｙｌｓｉｌａｎｅ、ＶＳ）とアクリルモノマー（ａｃｒｙｌｉｃ ｍｏｎｏｍｅｒ、ＡＭ）を反応モノマーとし、有機溶剤を使用しない環境下で過酸化物により重合反応を開始させ、共重合体（ＶＳ−ＡＭ ｃｏｐｏｌｙｍｅｒ）を生成した。反応式を式（１）に示す。そのうち、ビニルシランはトリメトキシビニルシラン（ｔｒｉｍｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）、またはトリエトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌ ｓｉｌａｎｅ）を採用する。アクリルモノマーはアクリル酸メチル、メタクリル酸メチル、またはメタクリル酸ヒドロキシエチルである。
1. Modification of acrylic monomer Using vinylsilane (VS) and acrylic monomer (AM) as reaction monomers, a polymerization reaction is initiated by peroxide in an environment that does not use an organic solvent. -AM copolymer) was generated. The reaction formula is shown in Formula (1). Among them, as the vinyl silane, trimethoxyvinyl silane or triethoxy vinyl silane is adopted. The acrylic monomer is methyl acrylate, methyl methacrylate, or hydroxyethyl methacrylate.
二、ナノ伝熱材を添加して改質アクリルモノマー上に接合させる
有機材料中に、高伝熱性質を持つナノ無機粉体を加える。前記ナノ無機粉体は、アルミナ（Ａｌ２Ｏ３）、窒化アルミニウム（ＡｌＮ）、窒化ホウ素（ＢＮ）、または炭化ケイ素（ＳｉＣ）を含み、有機材料の伝熱性を効果的に高め、高伝熱複合材料を製造することができる。本研究で合成した共重合体とナノ伝熱材は化学結合を形成することができ、その反応式を式（２）に示す。高伝熱性質の無機粉体と有機基材の相容性を効果的に増進することができる。
2. Add nano heat transfer material and bond it onto the modified acrylic monomer Add nano inorganic powder with high heat transfer properties to the organic material. The nano-inorganic powder includes alumina (Al 2 O 3 ), aluminum nitride (AlN), boron nitride (BN), or silicon carbide (SiC), and effectively enhances the heat transfer property of the organic material, thereby achieving high heat transfer. Composite materials can be manufactured. The copolymer synthesized in this study and the nano heat transfer material can form chemical bonds, and the reaction formula is shown in Equation (2). It is possible to effectively enhance the compatibility between the inorganic powder having a high heat transfer property and the organic base material.
三、伝熱骨格層を備えた相変化マイクロカプセルの製造
伝熱骨格層を備えた相変化マイクロカプセルは、相変化材料を芯、共重合体を骨格とし、その製造の流れは次の通りである。
（１）図１に示すように、工程Ｓ１１０では、アクリルモノマーとビニルシランを用意する。
（２）図１に示すように、工程Ｓ１２０では、アクリルモノマーとビニルシランを撹拌して混合し、第一溶液を形成する。そのうち、ビニルシランはトリメトキシビニルシラン（ｔｒｉｍｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）またはトリエトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌ ｓｉｌａｎｅ）等である。
（３）図１に示すように、工程Ｓ１３０では、工程Ｓ１２０で混合された混合物に、開始剤として微量の過酸化ベンゾイルを加え、油浴加熱下でプレ重合を行う。
（４）図１に示すように、工程Ｓ１４０では、相変化材料を用意する。
（５）図１に示すように、工程Ｓ１５０では、水溶液を加熱してポリビニルアルコールを溶解させ、ポリビニルアルコール水溶液を形成する。
（６）図１に示すように、工程Ｓ１６０では、相変化材料を工程Ｓ１５０で調製を完了したポリビニルアルコール水溶液に加え、温度を上昇させて相変化材料の融点を超過させ、液化動作を行い、その後液化した溶液を均一に撹拌する。
（７）図１に示すように、工程Ｓ１７０では、工程Ｓ１３０の反応を経た後のＰＭＭＡプレポリマーと工程Ｓ１６０の反応後の溶液を混合し、エチレングリコールジメタクリレートと伝熱材料（例えば窒化アルミニウム、窒化ホウ素、アルミナまたは炭化ケイ素）を加え、撹拌して分散させ、伝熱骨格層を備えた相変化マイクロカプセル溶液を形成する。
（８）図１に示すように、工程Ｓ１８０では、工程Ｓ１７０で形成された伝熱骨格層を備えた相変化マイクロカプセル溶液に開始剤として過酸化ベンゾイルを加え、油浴加熱でマイクロカプセルの重合被覆を完了する。
（９）図１に示すように、工程Ｓ１９０では、工程Ｓ１８０の処理を経た後のマイクロカプセルを氷浴、遠心、濾過後、下層のマイクロカプセルを乾燥させ、伝熱骨格層を備えた相変化マイクロカプセルを得る。
3. Manufacture of phase change microcapsules with heat transfer skeleton layer Phase change microcapsules with heat transfer skeleton layer have phase change material as core and copolymer as skeleton. is there.
(1) As shown in FIG. 1, in step S110, an acrylic monomer and vinyl silane are prepared.
(2) As shown in FIG. 1, in step S120, the acrylic monomer and vinyl silane are stirred and mixed to form a first solution. Among them, the vinyl silane is trimethoxyvinyl silane or triethoxy vinyl silane.
(3) As shown in FIG. 1, in step S130, a small amount of benzoyl peroxide is added as an initiator to the mixture mixed in step S120, and pre-polymerization is performed under oil bath heating.
(4) As shown in FIG. 1, in step S140, a phase change material is prepared.
(5) As shown in FIG. 1, in step S150, the aqueous solution is heated to dissolve the polyvinyl alcohol to form an aqueous polyvinyl alcohol solution.
(6) As shown in FIG. 1, in step S160, the phase change material is added to the polyvinyl alcohol aqueous solution prepared in step S150, the temperature is raised to exceed the melting point of the phase change material, and a liquefaction operation is performed. Thereafter, the liquefied solution is stirred uniformly.
(7) As shown in FIG. 1, in step S170, the PMMA prepolymer after the reaction in step S130 and the solution after the reaction in step S160 are mixed, and ethylene glycol dimethacrylate and a heat transfer material (for example, aluminum nitride, Boron nitride, alumina or silicon carbide) is added and stirred to disperse to form a phase change microcapsule solution with a heat transfer skeleton layer.
(8) As shown in FIG. 1, in step S180, benzoyl peroxide is added as an initiator to the phase change microcapsule solution provided with the heat transfer skeleton layer formed in step S170, and the microcapsules are polymerized by heating in an oil bath. Complete the coating.
(9) As shown in FIG. 1, in step S190, the microcapsules after the processing in step S180 are subjected to an ice bath, centrifugation, and filtration, and then the lower microcapsules are dried to provide a phase change provided with a heat transfer skeleton layer. Obtain microcapsules.
本発明の相変化材料は有機相変化材料であり、前記有機相変化材料は主に脂肪族高級炭化水素、高級脂肪酸、高級脂肪酸エステル、高級脂肪酸の塩、高級脂肪族アルコール、芳香族炭化水素、芳香族ケトン、芳香族アミド、及びその混合物から構成される群であるが、上述の有機相変化材料に限定されない。 The phase change material of the present invention is an organic phase change material, and the organic phase change material is mainly an aliphatic higher hydrocarbon, a higher fatty acid, a higher fatty acid ester, a salt of a higher fatty acid, a higher aliphatic alcohol, an aromatic hydrocarbon, A group composed of aromatic ketones, aromatic amides, and mixtures thereof, but is not limited to the organic phase change materials described above.
脂肪族高級炭化水素は通常６個以上の炭素原子を含む脂肪炭化水素であり、６〜３６個の炭素原子が好ましい。高級脂肪族アルコールは通常６個以上の炭素原子を含む脂肪炭化水素であり、６〜３６個の炭素原子が好ましい。 The aliphatic higher hydrocarbons are usually aliphatic hydrocarbons containing 6 or more carbon atoms, preferably 6 to 36 carbon atoms. The higher aliphatic alcohols are usually aliphatic hydrocarbons containing 6 or more carbon atoms, with 6 to 36 carbon atoms being preferred.
上述の製造方法のうち、アクリルモノマーとビニルシランの当量比は、１０：１〜１０：３が好ましい。 Among the above-described production methods, the equivalent ratio of the acrylic monomer and vinyl silane is preferably 10: 1 to 10: 3.
上述の製造方法のうち、前記相変化マイクロカプセルは芯骨格材料であり、そのうち芯材は有機相変化材料である。 Among the manufacturing methods described above, the phase change microcapsule is a core skeleton material, of which the core material is an organic phase change material.
上述の製造方法のうち、前記相変化マイクロカプセルは芯骨格材料であり、そのうち骨格材はビニルシランとアクリルモノマーの共重合体である。 Among the manufacturing methods described above, the phase change microcapsule is a core skeleton material, and the skeleton material is a copolymer of vinylsilane and an acrylic monomer.
上述の製造方法のうち、撹拌は磁力撹拌機、モーター式撹拌器またはホモジナイザーを採用することが好ましい。 Among the above-mentioned production methods, it is preferable to employ a magnetic stirrer, a motor type stirrer or a homogenizer for stirring.
上述の製造方法のうち、前記相変化材料の添加比率は１０ｗｔ％〜４０ｗｔ％である。 Among the manufacturing methods described above, the addition ratio of the phase change material is 10 wt% to 40 wt%.
上述の製造方法のうち、前記高伝熱性ナノ無機粉体（アルミナ、窒化アルミニウム、窒化ホウ素、炭化ケイ素）の添加比率は１０ｗｔ％〜４０ｗｔ％である。 Among the manufacturing methods described above, the addition ratio of the highly heat conductive nano inorganic powder (alumina, aluminum nitride, boron nitride, silicon carbide) is 10 wt% to 40 wt%.
上述の製造方法のうち、工程Ｓ１３０中の前記加熱範囲は５０℃〜１２０℃が好ましい。 Among the manufacturing methods described above, the heating range in step S130 is preferably 50 ° C to 120 ° C.
上述の製造方法のうち、工程Ｓ１６０中の前記加熱範囲は４０℃〜８０℃が好ましい。 Among the manufacturing methods described above, the heating range in step S160 is preferably 40 ° C to 80 ° C.
上述の製造方法のうち、工程Ｓ１８０中の前記加熱範囲は５０℃〜１２０℃が好ましい。 Among the manufacturing methods described above, the heating range in step S180 is preferably 50 ° C to 120 ° C.
本発明の伝熱骨格層を備えた相変化マイクロカプセルの製造方法は、従来のマイクロカプセル膜材の熱伝達係数が非常に低く、熱伝達の速度が低下する問題を効果的に解決することができる。 The manufacturing method of the phase change microcapsule having the heat transfer skeleton layer of the present invention can effectively solve the problem that the heat transfer coefficient of the conventional microcapsule membrane material is very low and the speed of heat transfer is reduced. it can.
以下、特定の具体的な実施例に基づいて、本発明の実施方法を説明し、当業者が本明細書の開示内容に基づいて本発明のその他の利点と効果を容易に理解できるようにする。 In the following, a method for carrying out the present invention will be described based on specific specific embodiments so that those skilled in the art can easily understand other advantages and effects of the present invention based on the disclosure of the present specification. .
本実施例は、メタクリル酸メチルに過酸化ベンゾイルを加え、油浴加熱下で重合し、プレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートを加え、油浴加熱下で均一に撹拌する。氷浴、遠心、濾過プロセスを経て、上層のマイクロカプセルを乾燥させ、相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．２０００Ｗ／ｍｋと測定された。 In this example, benzoyl peroxide is added to methyl methacrylate and polymerized under heating in an oil bath to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and stir uniformly under oil bath heating. Through an ice bath, centrifugation, and filtration process, the upper microcapsules are dried to obtain phase change microcapsules. The heat transfer coefficient of this microcapsule was measured to be 0.2000 W / mk.
本実施例はメタクリル酸メチル及びビニルシランのトリメトキシビニルシラン（ｔｒｉｍｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合し、プレポリマー溶液を得る。別にメタクリル酸メチルを重量比３:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートを加え、油浴加熱下で均一に撹拌する。氷浴、遠心、濾過を経て、上層のマイクロカプセルを乾燥させ、相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．１９８８Ｗ／ｍｋと測定された。かつ、その３０℃から８０℃までの温度上昇に必要な時間は３２５秒であり、８０℃から３０℃までの温度低下に必要な時間は３６５秒と測定された。 In this example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Add benzoyl peroxide and polymerize under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate having a weight ratio of 3: 1 paraffin wax (organic phase change material) is added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of the paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and stir uniformly under oil bath heating. Through an ice bath, centrifugation, and filtration, the upper microcapsules are dried to obtain phase change microcapsules. The heat transfer coefficient of this microcapsule was measured to be 0.1988 W / mk. The time required for the temperature increase from 30 ° C. to 80 ° C. was 325 seconds, and the time required for the temperature decrease from 80 ° C. to 30 ° C. was measured as 365 seconds.
本実施例はメタクリル酸メチルとビニルシランのトリメトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合してプレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートを加え、油浴加熱下で均一に撹拌する。氷浴、遠心、濾過を経て、上層のマイクロカプセルを乾燥させ、相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．１９９６Ｗ／ｍｋと測定された。かつ、その３０℃から８０℃までの温度上昇に必要な時間は３０３秒であり、８０℃から３０℃までの温度低下に必要な時間は３４８秒と測定された。 In this example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Benzoyl peroxide is added and polymerized under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and stir uniformly under oil bath heating. Through an ice bath, centrifugation, and filtration, the upper microcapsules are dried to obtain phase change microcapsules. The heat transfer coefficient of this microcapsule was measured to be 0.1996 W / mk. The time required for the temperature increase from 30 ° C. to 80 ° C. was 303 seconds, and the time required for the temperature decrease from 80 ° C. to 30 ° C. was measured as 348 seconds.
本実施例係はメタクリル酸メチル及びビニルシランのトリメトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合してプレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレート及びアルミナを加え、油浴加熱下で均一に撹拌する。そのうちアルミナの添加比率はメタクリル酸メチルとの重量比が１:２である。氷浴、遠心、濾過後、下層のマイクロカプセルを乾燥させ、本発明の伝熱骨格層を備えた相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．３５３５Ｗ／ｍｋと測定された。かつ、８０℃から３０℃までの温度低下に必要な時間は２６７秒と測定された。 In this example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Benzoyl peroxide is added and polymerized under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and alumina and stir uniformly under oil bath heating. Among them, the weight ratio of alumina to methyl methacrylate is 1: 2. After the ice bath, centrifugation, and filtration, the lower microcapsules are dried to obtain phase change microcapsules having the heat transfer skeleton layer of the present invention. The heat transfer coefficient of this microcapsule was measured to be 0.3535 W / mk. And the time required for the temperature fall from 80 degreeC to 30 degreeC was measured with 267 second.
本実施例はメタクリル酸メチルとビニルシランのトリメトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合し、プレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートと窒化アルミニウムを加え、油浴加熱下で均一に撹拌する。そのうち、窒化アルミニウムの添加比率はメタクリル酸メチルとの重量比が１:２である。氷浴、遠心、濾過後、下層のマイクロカプセルを乾燥させ、本発明の伝熱骨格層を備えた相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．４３１７Ｗ／ｍｋと測定された。かつ、３０℃から８０℃までの温度上昇に必要な時間はわずか１５９秒であり、８０℃から３０℃までの温度低下に必要な時間はわずか２０１秒と測定された。 In this example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Add benzoyl peroxide and polymerize under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and aluminum nitride and stir uniformly under oil bath heating. Among them, the addition ratio of aluminum nitride is 1: 2 by weight with respect to methyl methacrylate. After the ice bath, centrifugation, and filtration, the lower microcapsules are dried to obtain phase change microcapsules having the heat transfer skeleton layer of the present invention. The heat transfer coefficient of this microcapsule was measured to be 0.4317 W / mk. And the time required for the temperature increase from 30 ° C. to 80 ° C. was only 159 seconds, and the time required for the temperature decrease from 80 ° C. to 30 ° C. was only 201 seconds.
本実施例はメタクリル酸メチルとビニルシランのトリメトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合し、プレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートと窒化ホウ素を加え、油浴加熱下で均一に撹拌する。そのうち、酸化ホウ素の添加比率はメタクリル酸メチルとの重量比が１:２である。氷浴、遠心、濾過後、下層のマイクロカプセルを乾燥させ、本発明の伝熱骨格層を備えた相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．４２５８Ｗ／ｍｋと測定された。かつ、３０℃から８０℃までの温度上昇に必要な時間はわずか１７５秒であり、８０℃から３０℃までの温度低下に必要な時間はわずか２２６秒と測定された。 In this example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Add benzoyl peroxide and polymerize under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and boron nitride and stir uniformly under oil bath heating. Among them, the addition ratio of boron oxide is 1: 2 in weight ratio with methyl methacrylate. After the ice bath, centrifugation, and filtration, the lower microcapsules are dried to obtain phase change microcapsules having the heat transfer skeleton layer of the present invention. The heat transfer coefficient of this microcapsule was measured to be 0.4258 W / mk. In addition, the time required for the temperature increase from 30 ° C. to 80 ° C. was only 175 seconds, and the time required for the temperature decrease from 80 ° C. to 30 ° C. was only 226 seconds.
上述の実施例１〜５で得た伝熱骨格層を備えた相変化マイクロカプセルを、図２から図５に示す。そのうち図２は本発明の伝熱骨格層を備えた相変化マイクロカプセルの構造図であり、図３は本発明の実施例の走査式電子顕微鏡分析図であり、図４は実施例の走査式電子顕微鏡分析図である。 The phase change microcapsules provided with the heat transfer skeleton layers obtained in the above Examples 1 to 5 are shown in FIGS. 2 is a structural diagram of a phase change microcapsule having a heat transfer skeleton layer of the present invention, FIG. 3 is a scanning electron microscope analysis diagram of an embodiment of the present invention, and FIG. 4 is a scanning formula of the embodiment. It is an electron microscope analysis figure.
図２に示すように、本発明の伝熱骨格層を備えた相変化マイクロカプセルは相変化材料２１０と、前記相変化材料２１０を被覆する伝熱骨格層２２０を含み、そのうち、前記伝熱骨格層２２０はビニルシランとアクリルモノマー共重合体２３０、及び伝熱材２４０を含む。
As shown in FIG. 2, the phase change microcapsule having the heat transfer skeleton layer of the present invention includes a
Ｓ１１０〜Ｓ１９０ 工程
２１０ 相変化材料
２２０ 伝熱骨格層
２３０ ビニルシランとアクリルモノマー共重合体
２４０ 伝熱材
Steps S110 to
本発明は相変化マイクロカプセルの膜材中にナノ伝熱材料を加える製造方法に関し、特に、相変化マイクロカプセルの膜材中に高伝熱性のナノ伝熱材料を加える製造方法に関する。まずビニルシランとアクリルモノマーを採用した重合で共重合体を生成した後、無機伝熱材料を加え、相変化材料を芯とし、伝熱材料を含む共重合体を骨格とした相変化マイクロカプセルを製造して、これにより伝熱骨格層を備えた相変化マイクロカプセルの製造という目的を達する。 The present invention relates to a manufacturing method of adding a nano heat transfer material into a film material of phase change microcapsules, and more particularly to a manufacturing method of adding a highly heat transfer nano heat transfer material into a film material of phase change microcapsules. First, a copolymer is produced by polymerization using vinyl silane and acrylic monomer, and then an inorganic heat transfer material is added to produce phase change microcapsules with the phase change material as the core and the copolymer containing the heat transfer material as the skeleton. Thus, the objective of producing phase change microcapsules with a heat transfer skeleton layer is achieved.
既知の通り、相変化材料（Ｐｈａｓｅ ｃｈａｎｇｅ ｍａｔｅｒｉａｌｓ、ＰＣＭ）は固相から液相に、または液相から固相に変化可能な物質であり、かつ相変化の発生時に大量の潜熱の吸収または放出を伴い、相変化材料の最大の特徴は、それが大量の潜熱を吸収または放出するとき、システムの温度を変化なく、または小さい変化範囲で維持できることにある。一般に相変化材料を応用するときは、その相変化時により多くの熱を吸収または放出できる潜熱値が比較的大きい相変化材料を選択することで、よりよい効果が得られる。しかし、相変化材料を直接応用すると、相変化の過程で溶融のために材料の漏洩及び損失が発生し、材料の使用寿命が短縮される。マイクロカプセルは微量の物質を骨格層とする方式で別の材料の表面を包み込む技術であり、マイクロカプセル技術を利用することで、相変化材料の溶融時に生じる体積変化と材料漏洩の問題を回避することができる。このほか、マイクロカプセル化後の材料は粒径が小さく、比表面積が大きいため、より大きな伝熱面積を提供する。 As is known, phase change materials (PCM) are substances that can change from the solid phase to the liquid phase, or from the liquid phase to the solid phase, and absorb or release a large amount of latent heat when the phase change occurs. Accordingly, the greatest feature of a phase change material is that when it absorbs or releases a large amount of latent heat, the temperature of the system can be kept unchanged or in a small range of change. In general, when a phase change material is applied, a better effect can be obtained by selecting a phase change material having a relatively large latent heat value that can absorb or release more heat during the phase change. However, if the phase change material is applied directly, leakage and loss of the material occur due to melting in the process of phase change, and the service life of the material is shortened. Microcapsule is a technology that envelops the surface of another material by using a small amount of substance as a skeletal layer. By using microcapsule technology, the problem of volume change and material leakage that occurs when the phase change material melts is avoided. be able to. In addition, since the material after microencapsulation has a small particle size and a large specific surface area, it provides a larger heat transfer area.
しかしながら、マイクロカプセル膜材は多くが有機高分子材料であり、その熱伝達係数が非常に低いため、膜材は相変化材料の漏洩を防止することはできるものの、熱の伝達速度を低下させてしまう。 However, many of the microcapsule membrane materials are organic polymer materials, and their heat transfer coefficient is very low, so the membrane materials can prevent the leakage of phase change materials, but reduce the heat transfer rate. End up.
従来のマイクロカプセル膜材の熱伝達係数が非常に低く、熱の伝達速度が低下する問題を解決するため、本発明の目的は、伝熱骨格層を備えた相変化マイクロカプセルの製造方法を提供することにある。 In order to solve the problem that the heat transfer coefficient of the conventional microcapsule membrane material is very low and the heat transfer rate is lowered, an object of the present invention is to provide a method of manufacturing a phase change microcapsule having a heat transfer skeleton layer There is to do.
上述の目的及びその他の目的を達するため、本発明の伝熱骨格層を備えた相変化マイクロカプセルの製造方法は、膜材中にナノ伝熱材料を加えることでその熱伝達係数を高め、相変化材料の熱の放出または吸収を加速し、効果的な伝熱、放熱、エネルギー貯蔵等の効果を達するとともに、まずビニルシランとアクリルモノマーを重合して共重合体を生成した後、ナノ伝熱材を加えると、ナノ伝熱材表面の極性官能基がビニルシランと縮合して化学結合を形成するため、ナノ伝熱材料と共重合体の相容性が大幅に向上され、同時にマイクロカプセルで相変化複合材料を被覆する二段階プロセス（塊状重合と乳化重合）でナノ伝熱材料を安定的に分散させることができ、伝熱骨格層を備えた相変化マイクロカプセルを製造することができる。 In order to achieve the above-mentioned object and other objects, the method of manufacturing a phase change microcapsule having the heat transfer skeleton layer of the present invention increases the heat transfer coefficient by adding a nano heat transfer material in the film material, Accelerates the release or absorption of heat from the change material, achieves effective heat transfer, heat dissipation, energy storage, etc., and first forms a copolymer by polymerizing vinyl silane and acrylic monomer, then nano heat transfer material Is added, the polar functional group on the surface of the nano heat transfer material is condensed with vinyl silane to form a chemical bond, which greatly improves the compatibility of the nano heat transfer material and the copolymer, and at the same time changes the phase in the microcapsule. The nano heat transfer material can be stably dispersed by a two-step process (bulk polymerization and emulsion polymerization) for coating the composite material, and phase change microcapsules having a heat transfer skeleton layer can be manufactured.
本発明の製造の流れは次の通りである。 The manufacturing flow of the present invention is as follows.
一、アクリルモノマーの改質
ビニルシラン（ｖｉｎｙｌｓｉｌａｎｅ、ＶＳ）とアクリルモノマー（ａｃｒｙｌｉｃ
ｍｏｎｏｍｅｒ、ＡＭ）を反応モノマーとし、有機溶剤を使用しない環境下で過酸化物により重合反応を開始させ、共重合体（ＶＳ−ＡＭ ｃｏｐｏｌｙｍｅｒ）を生成した。反応式を式（１）に示す。そのうち、ビニルシランはトリメトキシビニルシラン（ｔｒｉｍｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）、またはトリエトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌ ｓｉｌａｎｅ）を採用する。アクリルモノマーはアクリル酸メチル、メタクリル酸メチル、またはメタクリル酸ヒドロキシエチルである。
1. Modification of acrylic monomer Vinylsilane (VS) and acrylic monomer (acrylic)
Monomer, AM) was used as a reaction monomer, and the polymerization reaction was initiated by peroxide in an environment where no organic solvent was used, to produce a copolymer (VS-AM copolymer). The reaction formula is shown in Formula (1). Among them, as the vinyl silane, trimethoxyvinyl silane or triethoxy vinyl silane is adopted. The acrylic monomer is methyl acrylate, methyl methacrylate, or hydroxyethyl methacrylate.
二、ナノ伝熱材を添加して改質アクリルモノマー上に接合させる
有機材料中に、高伝熱性質を持つナノ無機粉体を加える。前記ナノ無機粉体は、アルミナ（Ａｌ２Ｏ３）、窒化アルミニウム（ＡｌＮ）、窒化ホウ素（ＢＮ）、または炭化ケイ素（ＳｉＣ）を含み、有機材料の伝熱性を効果的に高め、高伝熱複合材料を製造することができる。本研究で合成した共重合体とナノ伝熱材は化学結合を形成することができ、その反応式を式（２）に示す。高伝熱性質の無機粉体と有機基材の相容性を効果的に増進することができる。
2. Add nano heat transfer material and bond it onto the modified acrylic monomer Add nano inorganic powder with high heat transfer properties to the organic material. The nano-inorganic powder includes alumina (Al 2 O 3 ), aluminum nitride (AlN), boron nitride (BN), or silicon carbide (SiC), and effectively enhances the heat transfer property of the organic material, thereby achieving high heat transfer. Composite materials can be manufactured. The copolymer synthesized in this study and the nano heat transfer material can form chemical bonds, and the reaction formula is shown in Equation (2). It is possible to effectively enhance the compatibility between the inorganic powder having a high heat transfer property and the organic base material.
三、伝熱骨格層を備えた相変化マイクロカプセルの製造
伝熱骨格層を備えた相変化マイクロカプセルは、相変化材料を芯、共重合体を骨格とし、その製造の流れは次の通りである。
（１）図１に示すように、工程Ｓ１１０では、アクリルモノマーとビニルシランを用意する。
（２）図１に示すように、工程Ｓ１２０では、アクリルモノマーとビニルシランを撹拌して混合し、第一溶液を形成する。そのうち、ビニルシランはトリメトキシビニルシラン（ｔｒｉｍｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）またはトリエトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌ ｓｉｌａｎｅ）等である。
（３）図１に示すように、工程Ｓ１３０では、工程Ｓ１２０で混合された混合物に、開始剤として微量の過酸化ベンゾイルを加え、油浴加熱下でプレ重合を行う。
（４）図１に示すように、工程Ｓ１４０では、相変化材料を用意する。
（５）図１に示すように、工程Ｓ１５０では、水溶液を加熱してポリビニルアルコールを溶解させ、ポリビニルアルコール水溶液を形成する。
（６）図１に示すように、工程Ｓ１６０では、相変化材料を工程Ｓ１５０で調製を完了したポリビニルアルコール水溶液に加え、温度を上昇させて相変化材料の融点を超過させ、液化動作を行い、その後液化した溶液を均一に撹拌する。
（７）図１に示すように、工程Ｓ１７０では、工程Ｓ１３０の反応を経た後のＰＭＭＡプレポリマーと工程Ｓ１６０の反応後の溶液を混合し、エチレングリコールジメタクリレートと伝熱材料（例えば窒化アルミニウム、窒化ホウ素、アルミナまたは炭化ケイ素）を加え、撹拌して分散させ、伝熱骨格層を備えた相変化マイクロカプセル溶液を形成する。
（８）図１に示すように、工程Ｓ１８０では、工程Ｓ１７０で形成された伝熱骨格層を備えた相変化マイクロカプセル溶液に開始剤として過酸化ベンゾイルを加え、油浴加熱でマイクロカプセルの重合被覆を完了する。
（９）図１に示すように、工程Ｓ１９０では、工程Ｓ１８０の処理を経た後のマイクロカプセルを氷浴、遠心、濾過後、下層のマイクロカプセルを乾燥させ、伝熱骨格層を備えた相変化マイクロカプセルを得る。
3. Manufacture of phase change microcapsules with heat transfer skeleton layer Phase change microcapsules with heat transfer skeleton layer have phase change material as core and copolymer as skeleton. is there.
(1) As shown in FIG. 1, in step S110, an acrylic monomer and vinyl silane are prepared.
(2) As shown in FIG. 1, in step S120, the acrylic monomer and vinyl silane are stirred and mixed to form a first solution. Among them, the vinyl silane is trimethoxyvinyl silane or triethoxy vinyl silane.
(3) As shown in FIG. 1, in step S130, a small amount of benzoyl peroxide is added as an initiator to the mixture mixed in step S120, and pre-polymerization is performed under oil bath heating.
(4) As shown in FIG. 1, in step S140, a phase change material is prepared.
(5) As shown in FIG. 1, in step S150, the aqueous solution is heated to dissolve the polyvinyl alcohol to form an aqueous polyvinyl alcohol solution.
(6) As shown in FIG. 1, in step S160, the phase change material is added to the polyvinyl alcohol aqueous solution prepared in step S150, the temperature is raised to exceed the melting point of the phase change material, and a liquefaction operation is performed. Thereafter, the liquefied solution is stirred uniformly.
(7) As shown in FIG. 1, in step S170, the PMMA prepolymer after the reaction in step S130 and the solution after the reaction in step S160 are mixed, and ethylene glycol dimethacrylate and a heat transfer material (for example, aluminum nitride, Boron nitride, alumina or silicon carbide) is added and stirred to disperse to form a phase change microcapsule solution with a heat transfer skeleton layer.
(8) As shown in FIG. 1, in step S180, benzoyl peroxide is added as an initiator to the phase change microcapsule solution provided with the heat transfer skeleton layer formed in step S170, and the microcapsules are polymerized by heating in an oil bath. Complete the coating.
(9) As shown in FIG. 1, in step S190, the microcapsules after the processing in step S180 are subjected to an ice bath, centrifugation, and filtration, and then the lower microcapsules are dried to provide a phase change provided with a heat transfer skeleton layer. Obtain microcapsules.
本発明の相変化材料は有機相変化材料であり、前記有機相変化材料は主に脂肪族高級炭化水素、高級脂肪酸、高級脂肪酸エステル、高級脂肪酸の塩、高級脂肪族アルコール、芳香族炭化水素、芳香族ケトン、芳香族アミド、及びその混合物から構成される群であるが、上述の有機相変化材料に限定されない。 The phase change material of the present invention is an organic phase change material, and the organic phase change material is mainly an aliphatic higher hydrocarbon, a higher fatty acid, a higher fatty acid ester, a salt of a higher fatty acid, a higher aliphatic alcohol, an aromatic hydrocarbon, A group composed of aromatic ketones, aromatic amides, and mixtures thereof, but is not limited to the organic phase change materials described above.
脂肪族高級炭化水素は通常６個以上の炭素原子を含む脂肪炭化水素であり、６〜３６個の炭素原子が好ましい。高級脂肪族アルコールは通常６個以上の炭素原子を含む脂肪炭化水素であり、６〜３６個の炭素原子が好ましい。 The aliphatic higher hydrocarbons are usually aliphatic hydrocarbons containing 6 or more carbon atoms, preferably 6 to 36 carbon atoms. The higher aliphatic alcohols are usually aliphatic hydrocarbons containing 6 or more carbon atoms, with 6 to 36 carbon atoms being preferred.
上述の製造方法のうち、アクリルモノマーとビニルシランの当量比は、１０：１〜１０：３が好ましい。 Among the above-described production methods, the equivalent ratio of the acrylic monomer and vinyl silane is preferably 10: 1 to 10: 3.
上述の製造方法のうち、前記相変化マイクロカプセルは芯骨格材料であり、そのうち芯材は有機相変化材料である。 Among the manufacturing methods described above, the phase change microcapsule is a core skeleton material, of which the core material is an organic phase change material.
上述の製造方法のうち、前記相変化マイクロカプセルは芯骨格材料であり、そのうち骨格材はビニルシランとアクリルモノマーの共重合体である。 Among the manufacturing methods described above, the phase change microcapsule is a core skeleton material, and the skeleton material is a copolymer of vinylsilane and an acrylic monomer.
上述の製造方法のうち、撹拌は磁力撹拌機、モーター式撹拌器またはホモジナイザーを採用することが好ましい。 Among the above-mentioned production methods, it is preferable to employ a magnetic stirrer, a motor type stirrer or a homogenizer for stirring.
上述の製造方法のうち、前記相変化材料の添加比率は１０ｗｔ％〜４０ｗｔ％である。 Among the manufacturing methods described above, the addition ratio of the phase change material is 10 wt% to 40 wt%.
上述の製造方法のうち、前記高伝熱性ナノ無機粉体（アルミナ、窒化アルミニウム、窒化ホウ素、炭化ケイ素）の添加比率は１０ｗｔ％〜４０ｗｔ％である。 Among the manufacturing methods described above, the addition ratio of the highly heat conductive nano inorganic powder (alumina, aluminum nitride, boron nitride, silicon carbide) is 10 wt% to 40 wt%.
上述の製造方法のうち、工程Ｓ１３０中の前記加熱範囲は５０℃〜１２０℃が好ましい。 Among the manufacturing methods described above, the heating range in step S130 is preferably 50 ° C to 120 ° C.
上述の製造方法のうち、工程Ｓ１６０中の前記加熱範囲は４０℃〜８０℃が好ましい。 Among the manufacturing methods described above, the heating range in step S160 is preferably 40 ° C to 80 ° C.
上述の製造方法のうち、工程Ｓ１８０中の前記加熱範囲は５０℃〜１２０℃が好ましい。 Among the manufacturing methods described above, the heating range in step S180 is preferably 50 ° C to 120 ° C.
本発明の伝熱骨格層を備えた相変化マイクロカプセルの製造方法は、従来のマイクロカプセル膜材の熱伝達係数が非常に低く、熱伝達の速度が低下する問題を効果的に解決することができる。 The manufacturing method of the phase change microcapsule having the heat transfer skeleton layer of the present invention can effectively solve the problem that the heat transfer coefficient of the conventional microcapsule membrane material is very low and the speed of heat transfer is reduced. it can.
以下、特定の具体的な実施例に基づいて、本発明の実施方法を説明し、当業者が本明細書の開示内容に基づいて本発明のその他の利点と効果を容易に理解できるようにする。 In the following, a method for carrying out the present invention will be described based on specific specific embodiments so that those skilled in the art can easily understand other advantages and effects of the present invention based on the disclosure of the present specification. .
本比較例は、メタクリル酸メチルに過酸化ベンゾイルを加え、油浴加熱下で重合し、プレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートを加え、油浴加熱下で均一に撹拌する。氷浴、遠心、濾過プロセスを経て、上層のマイクロカプセルを乾燥させ、相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．２０００Ｗ／ｍｋと測定された。 In this comparative example, benzoyl peroxide is added to methyl methacrylate and polymerized under heating in an oil bath to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and stir uniformly under oil bath heating. Through an ice bath, centrifugation, and filtration process, the upper microcapsules are dried to obtain phase change microcapsules. The heat transfer coefficient of this microcapsule was measured to be 0.2000 W / mk.
本比較例はメタクリル酸メチル及びビニルシランのトリメトキシビニルシラン（ｔｒｉｍｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合し、プレポリマー溶液を得る。別にメタクリル酸メチルを重量比３:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートを加え、油浴加熱下で均一に撹拌する。氷浴、遠心、濾過を経て、上層のマイクロカプセルを乾燥させ、相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．１９８８Ｗ／ｍｋと測定された。かつ、その３０℃から８０℃までの温度上昇に必要な時間は３２５秒であり、８０℃から３０℃までの温度低下に必要な時間は３６５秒と測定された。 In this comparative example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Add benzoyl peroxide and polymerize under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate having a weight ratio of 3: 1 paraffin wax (organic phase change material) is added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of the paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and stir uniformly under oil bath heating. Through an ice bath, centrifugation, and filtration, the upper microcapsules are dried to obtain phase change microcapsules. The heat transfer coefficient of this microcapsule was measured to be 0.1988 W / mk. The time required for the temperature increase from 30 ° C. to 80 ° C. was 325 seconds, and the time required for the temperature decrease from 80 ° C. to 30 ° C. was measured as 365 seconds.
本比較例はメタクリル酸メチルとビニルシランのトリメトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合してプレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートを加え、油浴加熱下で均一に撹拌する。氷浴、遠心、濾過を経て、上層のマイクロカプセルを乾燥させ、相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．１９９６Ｗ／ｍｋと測定された。かつ、その３０℃から８０℃までの温度上昇に必要な時間は３０３秒であり、８０℃から３０℃までの温度低下に必要な時間は３４８秒と測定された。 In this comparative example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Benzoyl peroxide is added and polymerized under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and stir uniformly under oil bath heating. Through an ice bath, centrifugation, and filtration, the upper microcapsules are dried to obtain phase change microcapsules. The heat transfer coefficient of this microcapsule was measured to be 0.1996 W / mk. The time required for the temperature increase from 30 ° C. to 80 ° C. was 303 seconds, and the time required for the temperature decrease from 80 ° C. to 30 ° C. was measured as 348 seconds.
本実施例係はメタクリル酸メチル及びビニルシランのトリメトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合してプレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレート及びアルミナを加え、油浴加熱下で均一に撹拌する。そのうちアルミナの添加比率はメタクリル酸メチルとの重量比が１:２である。氷浴、遠心、濾過後、下層のマイクロカプセルを乾燥させ、本発明の伝熱骨格層を備えた相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．３５３５Ｗ／ｍｋと測定された。かつ、８０℃から３０℃までの温度低下に必要な時間は２６７秒と測定された。 In this example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Benzoyl peroxide is added and polymerized under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and alumina and stir uniformly under oil bath heating. Among them, the weight ratio of alumina to methyl methacrylate is 1: 2. After the ice bath, centrifugation, and filtration, the lower microcapsules are dried to obtain phase change microcapsules having the heat transfer skeleton layer of the present invention. The heat transfer coefficient of this microcapsule was measured to be 0.3535 W / mk. And the time required for the temperature fall from 80 degreeC to 30 degreeC was measured with 267 second.
本実施例はメタクリル酸メチルとビニルシランのトリメトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合し、プレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートと窒化アルミニウムを加え、油浴加熱下で均一に撹拌する。そのうち、窒化アルミニウムの添加比率はメタクリル酸メチルとの重量比が１:２である。氷浴、遠心、濾過後、下層のマイクロカプセルを乾燥させ、本発明の伝熱骨格層を備えた相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．４３１７Ｗ／ｍｋと測定された。かつ、３０℃から８０℃までの温度上昇に必要な時間はわずか１５９秒であり、８０℃から３０℃までの温度低下に必要な時間はわずか２０１秒と測定された。 In this example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Add benzoyl peroxide and polymerize under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and aluminum nitride and stir uniformly under oil bath heating. Among them, the addition ratio of aluminum nitride is 1: 2 by weight with respect to methyl methacrylate. After the ice bath, centrifugation, and filtration, the lower microcapsules are dried to obtain phase change microcapsules having the heat transfer skeleton layer of the present invention. The heat transfer coefficient of this microcapsule was measured to be 0.4317 W / mk. And the time required for the temperature increase from 30 ° C. to 80 ° C. was only 159 seconds, and the time required for the temperature decrease from 80 ° C. to 30 ° C. was only 201 seconds.
本実施例はメタクリル酸メチルとビニルシランのトリメトキシビニルシラン（ｔｒｉｅｔｈｏｘｙｖｉｎｙｌｓｉｌａｎｅ）を当量比５:１で６０℃の油浴加熱下で混合する。過酸化ベンゾイルを加え、油浴加熱下で重合し、プレポリマー溶液を得る。別にメタクリル酸メチルと重量比１:１の石蝋（有機相変化材料）をポリビニルアルコール水溶液中に加え、石蝋の融点を超過するまで温度を上昇させて均一に撹拌する。プレポリマー溶液を入れ、均一に撹拌する。エチレングリコールジメタクリレートと窒化ホウ素を加え、油浴加熱下で均一に撹拌する。そのうち、酸化ホウ素の添加比率はメタクリル酸メチルとの重量比が１:２である。氷浴、遠心、濾過後、下層のマイクロカプセルを乾燥させ、本発明の伝熱骨格層を備えた相変化マイクロカプセルを得る。このマイクロカプセルの熱伝達係数は０．４２５８Ｗ／ｍｋと測定された。かつ、３０℃から８０℃までの温度上昇に必要な時間はわずか１７５秒であり、８０℃から３０℃までの温度低下に必要な時間はわずか２２６秒と測定された。 In this example, methyl methacrylate and trimethoxyvinylsilane of vinylsilane are mixed at an equivalent ratio of 5: 1 under heating in an oil bath at 60 ° C. Add benzoyl peroxide and polymerize under oil bath heating to obtain a prepolymer solution. Separately, methyl methacrylate and paraffin wax (organic phase change material) in a weight ratio of 1: 1 are added to an aqueous polyvinyl alcohol solution, and the temperature is raised until the melting point of paraffin wax is exceeded, and the mixture is stirred uniformly. Add the prepolymer solution and stir uniformly. Add ethylene glycol dimethacrylate and boron nitride and stir uniformly under oil bath heating. Among them, the addition ratio of boron oxide is 1: 2 in weight ratio with methyl methacrylate. After the ice bath, centrifugation, and filtration, the lower microcapsules are dried to obtain phase change microcapsules having the heat transfer skeleton layer of the present invention. The heat transfer coefficient of this microcapsule was measured to be 0.4258 W / mk. In addition, the time required for the temperature increase from 30 ° C. to 80 ° C. was only 175 seconds, and the time required for the temperature decrease from 80 ° C. to 30 ° C. was only 226 seconds.
上述の実施例１〜３で得た伝熱骨格層を備えた相変化マイクロカプセルを、図２から図４に示す。そのうち図２は本発明の伝熱骨格層を備えた相変化マイクロカプセルの構造図であり、図３は本発明の実施例の走査式電子顕微鏡分析図であり、図４は実施例の走査式電子顕微鏡分析図である。 The phase change microcapsules having a heat transfer skeleton layer obtained in Example 1 to 3 described above is shown in FIGS. 2-4. 2 is a structural diagram of a phase change microcapsule having a heat transfer skeleton layer of the present invention, FIG. 3 is a scanning electron microscope analysis diagram of an embodiment of the present invention, and FIG. 4 is a scanning formula of the embodiment. It is an electron microscope analysis figure.
図２に示すように、本発明の伝熱骨格層を備えた相変化マイクロカプセルは相変化材料２１０と、前記相変化材料２１０を被覆する伝熱骨格層２２０を含み、そのうち、前記伝熱骨格層２２０はビニルシランとアクリルモノマー共重合体２３０、及び伝熱材２４０を含む。
As shown in FIG. 2, the phase change microcapsule having the heat transfer skeleton layer of the present invention includes a
Ｓ１１０〜Ｓ１９０ 工程
２１０ 相変化材料
２２０ 伝熱骨格層
２３０ ビニルシランとアクリルモノマー共重合体
２４０ 伝熱材
Steps S110 to
Claims (15)
（Ａ）ビニルシランを用意する工程と、
（Ｂ）前記ビニルシラン中にアクリルモノマーを加え、開始剤として微量の過酸化ベンゾイルを加え、油浴加熱下で撹拌してプレ重合反応を行い、第一溶液を形成する工程と、
（Ｃ）相変化材料をポリビニルアルコール水溶液に加え、相変化材料の融点を超えるまで温度を上昇させて液化を行い、均一に撹拌して第二溶液を形成する工程と、
（Ｄ）前記第二溶液を前記第一溶液に加え、均一に撹拌する工程と、
（Ｅ）エチレングリコールジメタクリレート及び高伝熱性ナノ無機粉体を加え、さらに開始剤として過酸化ベンゾイルを加え、撹拌して油浴加熱し、マイクロカプセルの重合被覆を完了し、伝熱骨格層を備えた相変化マイクロカプセルを得る工程と、
を含むことを特徴とする、伝熱骨格層を備えた相変化マイクロカプセルの製造方法。 A method for producing a phase change microcapsule having a heat transfer skeleton layer, the method comprising:
(A) preparing vinyl silane;
(B) adding an acrylic monomer to the vinyl silane, adding a small amount of benzoyl peroxide as an initiator, stirring under oil bath heating to perform a prepolymerization reaction, and forming a first solution;
(C) adding a phase change material to an aqueous polyvinyl alcohol solution, increasing the temperature until the melting point of the phase change material is exceeded, liquefying, and stirring uniformly to form a second solution;
(D) adding the second solution to the first solution and stirring uniformly;
(E) Add ethylene glycol dimethacrylate and highly heat-conducting nano-inorganic powder, add benzoyl peroxide as an initiator, stir and heat in an oil bath to complete the microcapsule polymerization coating, Obtaining a phase change microcapsule comprising:
A process for producing phase change microcapsules having a heat transfer skeleton layer, comprising:
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