JPH0640952B2 - Manufacturing method of microcapsule containing heat storage material - Google Patents
Manufacturing method of microcapsule containing heat storage materialInfo
- Publication number
- JPH0640952B2 JPH0640952B2 JP61253156A JP25315686A JPH0640952B2 JP H0640952 B2 JPH0640952 B2 JP H0640952B2 JP 61253156 A JP61253156 A JP 61253156A JP 25315686 A JP25315686 A JP 25315686A JP H0640952 B2 JPH0640952 B2 JP H0640952B2
- Authority
- JP
- Japan
- Prior art keywords
- storage material
- heat storage
- monomer
- aqueous solution
- particle size
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 238000005338 heat storage Methods 0.000 title claims description 45
- 239000011232 storage material Substances 0.000 title claims description 41
- 239000003094 microcapsule Substances 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000002775 capsule Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 235000017281 sodium acetate Nutrition 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 14
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- -1 for example Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 2
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- LGLDSEPDYUTBNZ-UHFFFAOYSA-N 3-phenylbuta-1,3-dien-2-ylbenzene Chemical compound C=1C=CC=CC=1C(=C)C(=C)C1=CC=CC=C1 LGLDSEPDYUTBNZ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CGPCWCNESIXOGU-UHFFFAOYSA-L N(=O)[O-].[Na+].Cl(=O)(=O)(=O)[O-].[Na+] Chemical compound N(=O)[O-].[Na+].Cl(=O)(=O)(=O)[O-].[Na+] CGPCWCNESIXOGU-UHFFFAOYSA-L 0.000 description 1
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940018038 sodium carbonate decahydrate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
- F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
- F28D20/023—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、蓄熱材封入マイクロカプセルの製造法に関す
る。更に詳しくは、カプセル膜を重合法により形成せし
める蓄熱材封入マイクロカプセルの製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing microcapsules encapsulating a heat storage material. More specifically, it relates to a method for producing microcapsules encapsulating a heat storage material in which a capsule film is formed by a polymerization method.
〔従来の技術〕および〔発明が解決しようとする問題
点〕 蓄熱材と熱媒体との熱交換手段としては、直接接触によ
る方法が最も効率がよいが、蓄熱材と熱媒体とが物理
的、化学的に相互作用を生ずる場合が多く、そのため間
接接触を行わざるを得ない。[Prior Art] and [Problems to be Solved by the Invention] As the heat exchange means between the heat storage material and the heat medium, the method by direct contact is the most efficient, but the heat storage material and the heat medium are physically In many cases, they chemically interact with each other, so that indirect contact is unavoidable.
この間接熱交換手段としては、蓄熱材をカプセル化し、
カプセル膜を介して熱媒体と熱交換する方法が蓄熱材の
単位体積当りの表面積が大きくなるため有効であり、こ
の単位体積当りの表面積を大きくして伝熱促進をより有
効ならしめるために、カプセルのマイクロ化が望まれて
いる。As the indirect heat exchange means, a heat storage material is encapsulated,
A method of exchanging heat with the heat medium through the capsule membrane is effective because the surface area per unit volume of the heat storage material is large, and in order to increase the surface area per unit volume to make heat transfer promotion more effective, The miniaturization of capsules is desired.
しかしながら、カプセルに蓄熱材を封入する工程でカプ
セルをマイクロ化することは、それだけ高度な技術が必
要であり、製造コストの増加を招くため、実際上それの
マイクロ化には限界がみられた。また、一般のカプセル
化方法では、カプセル膜が化学反応によって形成される
ため、膜形成材料と反応性を有する場合の多い蓄熱材を
カプセル化することは困難であった。However, micronization of the capsule in the step of encapsulating the heat storage material in the capsule requires a higher level of technology, which leads to an increase in manufacturing cost, so that the micronization of the microcapsule is actually limited. Further, in a general encapsulation method, since the capsule film is formed by a chemical reaction, it is difficult to encapsulate the heat storage material, which is often reactive with the film forming material.
本発明者らは、このような問題点を有する蓄熱材のマイ
クロカプセル化方法について検討を重ねた結果、蓄熱材
に対して不活性な単量体を用いる重合法によってカプセ
ル膜を形成させることにより、かかる課題が効果的に解
決されることを見出した。As a result of repeated studies on the microencapsulation method of the heat storage material having such problems, the present inventors have found that by forming a capsule film by a polymerization method using a monomer inert to the heat storage material. , And found that such problems can be effectively solved.
〔問題点を解決するための手段〕および〔作用〕 従って、本発明は蓄熱材封入マイクロカプセルの製造法
に係り、蓄熱材封入マイクロカプセルの製造は、油溶性
界面活性剤を含有する、無機水和物蓄熱材に対して不活
性な単量体中にエマルジョンまたはけん濁液として分散
させた蓄熱材を水溶性界面活性剤水溶液中に滴下し、次
いで該水溶液中で分散状態にある蓄熱材の表面を覆って
いる単量体を重合開始剤の存在下で重合させ、カプセル
膜を形成させることにより行われ、得られた蓄熱材封入
マイクロカプセルは0.05μｍ〜0.5mmの粒径を有する。[Means for Solving Problems] and [Action] Accordingly, the present invention relates to a method for producing a heat storage material-encapsulating microcapsule, wherein the production of the heat storage material-encapsulating microcapsule includes an inorganic water containing an oil-soluble surfactant. The heat storage material dispersed as an emulsion or suspension in a monomer inert to the heat storage material is added dropwise to the aqueous solution of the water-soluble surfactant, and then the heat storage material dispersed in the aqueous solution is added. The heat-storage material-encapsulated microcapsules obtained by polymerizing the surface-covering monomer in the presence of a polymerization initiator to form a capsule film have a particle size of 0.05 μm to 0.5 mm.
この製造法においては、まず油溶性界面活性剤を含有す
る、蓄熱材に対して不活性な単量体中に分散させた蓄熱
材の調製が行われる。In this manufacturing method, first, a heat storage material containing an oil-soluble surfactant and dispersed in a monomer inert to the heat storage material is prepared.
蓄熱材としては、次のような融解温度（融点）を有する
無機水和物が用いられ、必要に応じて過冷却防止剤とし
ての発核剤と併用される。As the heat storage material, an inorganic hydrate having the following melting temperature (melting point) is used, and is optionally used in combination with a nucleating agent as a supercooling inhibitor.
塩化カルシウム・6水和物 29℃ 炭酸ナトリウム・10水和物 32℃ 硫酸ナトリウム・10水和物 〃 リン酸水素２ナトリウム・12水和物 36℃ 硝酸亜鉛・6水和物 〃 硝酸カルシウム・4水和物 45℃ チオ硫酸ナトリウム・5水和物 48℃ 硝酸ニッケル・6水和物 54℃ 酢酸ナトリウム・3水和物 58℃ これらの蓄熱材は、油溶性界面活性剤、一般には非イオ
ン界面活性剤を約0.5〜５重量％の濃度で含有する単量
体中に分散せしめる。この単量体は、蓄熱材に対して不
活性なものでなければならず、また水に不溶性の液体
で、その沸点は用いられる蓄熱材の融点以上のものであ
り、例えばスチレン、クロルスチレン、安息香酸アリ
ル、メタクリル酸ブチル、メタクリル酸イソブチル、メ
タクリル酸メチル、クロロプレン、2,3-ジフェニルブタ
ジエンなどの一官能性単量体またはこれとジビニルベン
ゼン、フタル酸ジアリル、イソフタル酸ジアリル、エチ
レングリコールジメタクリレート、ジエチレングリコー
ルビスアリルカーボネートなどの多官能性単量体との混
合物が用いられる。また単量体の沸点が蓄熱材の融点以
下であっても、それをオリゴマー化することにより融点
以上となるものも用いられる。Calcium chloride hexahydrate 29 ° C Sodium carbonate decahydrate 32 ° C Sodium sulfate decahydrate 〃 Disodium hydrogen phosphate dodecahydrate 36 ° C Zinc nitrate hexahydrate 〃 Calcium nitrate 4 Hydrate 45 ℃ Sodium thiosulfate pentahydrate 48 ℃ Nickel nitrate hexahydrate 54 ℃ Sodium acetate trihydrate 58 ℃ These heat storage materials are oil-soluble surfactants, generally nonionic interfaces. The active agent is dispersed in the monomer containing the concentration of about 0.5-5% by weight. This monomer must be inert to the heat storage material, and is a water-insoluble liquid, the boiling point of which is higher than the melting point of the heat storage material used, for example, styrene, chlorostyrene, Monofunctional monomers such as allyl benzoate, butyl methacrylate, isobutyl methacrylate, methyl methacrylate, chloroprene, and 2,3-diphenylbutadiene, or divinylbenzene, diallyl phthalate, diallyl isophthalate, ethylene glycol dimethacrylate. , A mixture with a polyfunctional monomer such as diethylene glycol bisallyl carbonate is used. Further, even if the boiling point of the monomer is not higher than the melting point of the heat storage material, it is also possible to use one which becomes higher than the melting point by oligomerizing it.
油溶性界面活性剤を含有する単量体中への蓄熱材の分散
は任意の方法で行なうことができ、例えば用いられる蓄
熱材の融解温度以上に加熱した単量体溶液中に同温度に
加熱した蓄熱材融液を攪拌下に滴下し、水相／有機相か
らなる一次エマルジョンを形成させることによって行わ
れ、あるいは蓄熱材粉末を単量体溶液中に攪拌下に添加
し、けん濁させるだけでもよい。Dispersion of the heat storage material in the monomer containing the oil-soluble surfactant can be carried out by any method, for example, heating to the same temperature in the monomer solution heated above the melting temperature of the heat storage material used. The heat storage material melt is added dropwise with stirring to form a primary emulsion consisting of an aqueous phase / organic phase, or the heat storage material powder is added to the monomer solution with stirring and suspended. But it's okay.
このようにして形成された蓄熱材の単量体分散液は、そ
れと同温度の水溶性界面活性剤水溶液中に攪拌下で滴下
される。水溶性界面活性剤としては、例えばドデシルス
ルホン酸ナトリウムなどの陰イオン界面活性剤やゼラチ
ンなどが用いられ、それの約0.5〜５％水溶液中へ上記
分散液の滴下が行われる。The monomer dispersion liquid of the heat storage material thus formed is dropped into the aqueous solution of the water-soluble surfactant at the same temperature as that under stirring. As the water-soluble surfactant, for example, an anionic surfactant such as sodium dodecyl sulfonate, gelatin, etc. are used, and the above dispersion liquid is dropped into an aqueous solution of about 0.5 to 5% thereof.
蓄熱材は、水溶液中に分散状態で存在するが、この表面
は単量体によって覆われているので、それを約0.1〜５
重量％の水溶性または油溶性の重合開始剤の存在下で重
合させるとカプセル膜が形成される。The heat storage material exists in an aqueous solution in a dispersed state, but since the surface of the heat storage material is covered with a monomer, it is added to about 0.1 to 5
Polymerization in the presence of wt% of a water-soluble or oil-soluble polymerization initiator forms a capsule film.
水溶性の重合開始剤としては、例えば過硫酸アンモニウ
ム、過硫酸カリウム、クメンヒドロペルオキシド、アゾ
ビスイソブチルアミジン塩酸塩、アゾビスシアノ吉草
酸、過酸化水素、過塩素酸ナトリウムなどが用いられ、
これらは例えば過酸化水素−第１鉄塩、過塩素酸ナトリ
ウム−亜硝酸ナトリウムのようにレドックス系としても
用いられる。水溶性重合開始剤の添加は、単量体中に分
散させた蓄熱材をそこに滴下させる水溶性界面活性剤水
溶液中または蓄熱材を滴下、分散させた水溶液中にいず
れであってもよく、あるいは蓄熱材の融液または粉末に
直接添加して用いることもできる。As the water-soluble polymerization initiator, for example, ammonium persulfate, potassium persulfate, cumene hydroperoxide, azobisisobutylamidine hydrochloride, azobiscyanovaleric acid, hydrogen peroxide, sodium perchlorate, etc. are used.
They are also used as a redox system such as hydrogen peroxide-ferrous salt, sodium perchlorate-sodium nitrite. The addition of the water-soluble polymerization initiator may be either in the aqueous solution of the water-soluble surfactant or the heat storage material, in which the heat storage material dispersed in the monomer is added dropwise, Alternatively, it can be used by directly adding it to the melt or powder of the heat storage material.
また、油溶性重合開始剤としては、例えば過酸化ベンゾ
イル、過酸化ラウロイル、ジイソプロピルパーオキシジ
カーボネート、ジシクロヘキシルパーオキシジカーボネ
ートなどの過酸化物系開始剤あるいはアゾビスイソブチ
ロニトリル、アゾビス-2、4-ジメチルバレロニトリル、
アゾビスシクロヘキサンカルボニトリルなどのアゾ系開
始剤が一般に用いられる。As the oil-soluble polymerization initiator, for example, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, peroxide initiators such as dicyclohexyl peroxydicarbonate or azobisisobutyronitrile, azobis-2, 4-dimethylvaleronitrile,
Azo initiators such as azobiscyclohexanecarbonitrile are commonly used.
これらの油溶性重合開始剤は、一般に単量体に添加して
用いられる。従って、一次エマルジョン形成時には、単
量体の加熱温度では分解せず、即ち単量体の重合を開始
させないような重合開始剤が選択して用いられる。These oil-soluble polymerization initiators are generally used by adding them to monomers. Therefore, at the time of forming the primary emulsion, a polymerization initiator that does not decompose at the heating temperature of the monomer, that is, does not start the polymerization of the monomer, is selected and used.
分散状態で水溶液中に存在する蓄熱材の表面を覆ってい
る単量体の重合は、このような重合開始剤の存在下にお
いて、所望の重合温度に加熱することにより行われ、カ
プセル膜を形成させて、そこに蓄熱材を封入させる。単
量体として多官能性単量体との混合物を用いた場合に
は、そこに形成されるマイクロカプセル膜は架橋構造を
有している。Polymerization of the monomer covering the surface of the heat storage material present in the aqueous solution in a dispersed state is carried out by heating at a desired polymerization temperature in the presence of such a polymerization initiator to form a capsule film. Then, the heat storage material is enclosed therein. When a mixture with a polyfunctional monomer is used as the monomer, the microcapsule film formed therein has a crosslinked structure.
本発明方法によれば、粒径約0.05μｍ〜0.5mm程度の蓄
熱材封入マイクロカプセルが容易に形成され、形成され
たカプセル膜は強固である。そして、このようなマイク
ロカプセル化された蓄熱材は、単位体積当りの表面積が
大きくなるので、蓄熱材と熱媒体との間の熱交換性能を
大幅に改善させる。According to the method of the present invention, the heat storage material-encapsulated microcapsules having a particle size of about 0.05 μm to 0.5 mm are easily formed, and the formed capsule film is strong. Further, such a microencapsulated heat storage material has a large surface area per unit volume, so that the heat exchange performance between the heat storage material and the heat medium is significantly improved.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１ スチレン50gおよびポリオキシエチレンオレイルエステ
ル２ｇの混合物を70℃に加熱した溶液に、やはり70℃に
加熱した酢酸ナトリウム・3水和物30ｇを攪拌下に滴下し
て、酢酸ナトリウム・3水和物融液のエマルジョンをスチ
レン中に形成させた。Example 1 To a solution obtained by heating a mixture of 50 g of styrene and 2 g of polyoxyethylene oleyl ester at 70 ° C., 30 g of sodium acetate trihydrate also heated at 70 ° C. was added dropwise with stirring to give sodium acetate / 3 water. An emulsion of the Japanese melt was formed in styrene.
このエマルジョン液を、ドデシルスルホン酸ナトリウム
10gを水300m中に溶解させ、70℃に加熱した水溶液中
に、攪拌下に滴下して二次エマルジョンを形成させ、そ
こに20％過硫酸アンモニウム水溶液５ｍを添加して、
攪拌下に80℃に５時間反応させた。This emulsion solution is treated with sodium dodecyl sulfonate.
Dissolve 10 g in 300 m of water and drop it with stirring into an aqueous solution heated to 70 ° C. to form a secondary emulsion, and add 5% of 20% ammonium persulfate aqueous solution thereto,
The mixture was reacted at 80 ° C for 5 hours with stirring.
この結果、酢酸ナトリウム・3水和物が封入されたポリス
チレンマイクロカプセル（粒径約0.05〜0.3mmが得られ
た。As a result, polystyrene microcapsules containing sodium acetate trihydrate (particle size of about 0.05-0.3 mm were obtained.
実施例２ 実施例１において、二次エマルジョン形成後に20％過硫
酸アンモニウム水溶液を添加する代りに、二次エマルジ
ョン形成に用いられた水溶液中に同量の過硫酸アンモニ
ウムを添加した。その結果、同じ粒径範囲の酢酸ナトリ
ウム・3水和物封入マイクロカプセルが得られた。Example 2 Instead of adding the 20% ammonium persulfate aqueous solution after the secondary emulsion formation in Example 1, the same amount of ammonium persulfate was added to the aqueous solution used for the secondary emulsion formation. As a result, sodium acetate trihydrate-encapsulated microcapsules with the same particle size range were obtained.
実施例３ スチレン50ｇおよびポリオキシエチレンオレイルエステ
ル２ｇの混合物を30℃に加熱した溶液に、平均粒径約0.
1mmに粉砕した酢酸ナトリウム・3水和物の粉末30ｇを攪
拌下に添加し、酢酸ナトリウム・3水和物のけん濁液を形
成させた。Example 3 A solution of a mixture of 50 g of styrene and 2 g of polyoxyethylene oleyl ester heated to 30 ° C. was added to a solution having an average particle size of about 0.1.
30 g of sodium acetate trihydrate powder crushed to 1 mm was added with stirring to form a suspension of sodium acetate trihydrate.
このけん濁液を、ドデシルスルホン酸ナトリウム10ｇお
よび30％過酸化水素水溶液５ｍを水300m中に溶解さ
せ、やはり30℃に加温した水溶液中に攪拌下に滴下し、
滴下終了後反応液の温度を50℃に上げてから、20％塩化
第１鉄水溶液７ｍを滴下して、攪拌状態を維続しなが
ら４時間反応させた。This suspension was dissolved in 10 g of sodium dodecyl sulfonate and 5 m of 30% hydrogen peroxide aqueous solution in 300 m of water, and the solution was also added dropwise to the aqueous solution heated to 30 ° C with stirring.
After the completion of the dropping, the temperature of the reaction solution was raised to 50 ° C., 7 m of 20% ferrous chloride aqueous solution was dropped, and the reaction was continued for 4 hours while maintaining the stirring state.
この結果、酢酸ナトリウム・3水和物が封入されたポリス
チレンのマイクロカプセル（粒径約0.1mm）が得られ
た。As a result, polystyrene microcapsules (particle size: about 0.1 mm) in which sodium acetate trihydrate was encapsulated were obtained.
実施例４ 実施例１において、20％過硫酸アンモニウム水溶液５ｍ
の代りに過硫酸アンモニウム１ｇを用い、それを酢酸
ナトリウム・3水和物融液中に添加して用いた。Example 4 In Example 1, 5% of 20% ammonium persulfate aqueous solution
1 g of ammonium persulfate was used instead of, and it was used by adding it to the sodium acetate trihydrate melt.
その結果、酢酸ナトリウム・3水和物が封入されたポリス
チレンマイクロカプセル（粒径約0.5〜５μｍ）が得ら
れた。As a result, polystyrene microcapsules (particle size: about 0.5 to 5 μm) in which sodium acetate trihydrate was encapsulated were obtained.
実施例５〜７ 実施例１〜４において、それぞれ酢酸ナトリウム・3水和
物と共に、それに対して１重量％のリン酸三ナトリウム
が発核剤として添加されて用いられた。Examples 5 to 7 In Examples 1 to 4, sodium acetate trihydrate was used together with 1% by weight of trisodium phosphate added as a nucleating agent.
いずれも、同様粒径のマイクロカプセルが得られた。In each case, microcapsules having the same particle size were obtained.
実施例８ 実施例１において、酢酸ナトリウム・3水和物の代りに同
量の塩化カルシウム・6水和物を用い、一次おび二次エマ
ルジョン形成を60℃で行なった。Example 8 In Example 1, the same amount of calcium chloride hexahydrate was used in place of sodium acetate trihydrate, and primary and secondary emulsion formation was carried out at 60 ° C.
この結果、塩化カルシウム・6水和物が封入されたポリス
チレンマイクロカプセル（粒径約0.05〜0.3mm）が得ら
れた。As a result, polystyrene microcapsules (particle size: about 0.05 to 0.3 mm) in which calcium chloride hexahydrate was encapsulated were obtained.
実施例９ スチレン40ｇ、ジビニルベンゼン10ｇ、過酸化ベンゾイ
ル0.5ｇおよびポリオキシエチレンオレイルエステル２
ｇの混合物を65℃に加熱した溶液に、やはり65℃に加熱
した酢酸ナトリウム・3水和物30ｇを攪拌下に滴下して、
酢酸ナトリウム・3水和物融液のエマルジョンをスチレン
−ジビニルベンゼン混合液中に形成させた。Example 9 40 g of styrene, 10 g of divinylbenzene, 0.5 g of benzoyl peroxide and polyoxyethylene oleyl ester 2
30 g of sodium acetate trihydrate, which was also heated to 65 ° C., was added dropwise to the solution obtained by heating the mixture of g to 65 ° C. with stirring,
An emulsion of sodium acetate trihydrate melt was formed in a styrene-divinylbenzene mixture.
このエマルジョン液を、ドデシルスルホン酸ナトリウム
10ｇを水300m中に溶解させ、65℃に加熱した水溶液中
に、攪拌下に滴下して二次エマルジョンを形成させ、更
に攪拌を継続しながら90℃に10時間加熱して、スチレン
およびジビニルベンゼンを共重合させた。This emulsion solution is treated with sodium dodecyl sulfonate.
Dissolve 10 g in 300 m of water and drop it into an aqueous solution heated to 65 ° C with stirring to form a secondary emulsion. While continuing stirring, heat to 90 ° C for 10 hours to add styrene and divinylbenzene. Was copolymerized.
この結果、酢酸ナトリウム・3水和物が封入された架橋ポ
リスチレンマイクロカプセル（粒径約0.05〜0.5mm）が
得られた。As a result, crosslinked polystyrene microcapsules (particle size: about 0.05 to 0.5 mm) in which sodium acetate trihydrate was encapsulated were obtained.
実施例１０ 実施例９において、スチレンの代りに安息香酸アリル
を、またジビニルベンゼンの代りにイソフタル酸ジアリ
ルをそれぞれ同量用いると、同様粒径の蓄熱材封入架橋
ポリ安息香酸アリルマイクロカプセルが得られた。Example 10 In Example 9, the same amount of allyl benzoate was used instead of styrene and diallyl isophthalate was used instead of divinylbenzene to obtain crosslinked polyallyl benzoate microcapsules encapsulating a heat storage material having the same particle size. It was
実施例１１〜１２ 実施例９〜１０において、過酸化ベンゾイルの代りにア
ゾビスイソブチロニトリル0.3ｇを用いると、いずれも
同様粒径の蓄熱材封入マイクロカプセルが得られた。Examples 11 to 12 In Examples 9 to 10, when 0.3 g of azobisisobutyronitrile was used in place of benzoyl peroxide, microcapsules encapsulating a heat storage material having the same particle size were obtained.
実施例１３ スチレン40ｇ、ジビニルベンゼン10ｇ、ジイソプロピル
パーオキシジカーボネート0.5ｇおよびポリオキシエチ
レンオレインエステル0.2ｇの混合物を30℃に加温した
溶液に、平均粒径約0.1mmに粉砕した酢酸ナトリウム・3
水和物の粉末30ｇを攪拌下に添加し、酢酸ナトリウム・3
水和物のけん濁液を形成させた。Example 13 A solution obtained by heating a mixture of 40 g of styrene, 10 g of divinylbenzene, 0.5 g of diisopropyl peroxydicarbonate and 0.2 g of polyoxyethylene olein ester to 30 ° C. and pulverizing sodium acetate 3 having an average particle size of about 0.1 mm.
Add 30 g of hydrate powder with stirring and add sodium acetate.3
A suspension of hydrate was formed.
このけん濁液を、ドデシルスルホン酸ナトリウム10ｇを
水300mに溶解させ、これを30℃に加温した水溶液中に
攪拌下に滴下し、滴下終了後液温を50℃に上げ、攪拌状
態を継続しながら５時間反応させ、スチレンおよびジビ
ニルベンゼンを共重合させた。This suspension was prepared by dissolving 10 g of sodium dodecyl sulfonate in 300 m of water and dropping it into an aqueous solution heated to 30 ° C with stirring. After completion of the dropping, the liquid temperature was raised to 50 ° C and the stirring state was continued. While reacting for 5 hours, styrene and divinylbenzene were copolymerized.
この結果、酢酸ナトリウム・3水和物が封入された架橋性
ポリスチレンマイクロカプセル（粒径約0.1mm）が得ら
れた。As a result, crosslinkable polystyrene microcapsules (particle size: about 0.1 mm) in which sodium acetate trihydrate was encapsulated were obtained.
Claims (1)
蓄熱材に対して不活性な単量体中にエマルジョンまたは
けん濁液として分散させた蓄熱材を、水溶性界面活性剤
水溶液中に滴下し、次いで該水溶液中で分散状態にある
蓄熱材の表面を覆っている単量体を重合開始剤の存在下
で重合させ、カプセル膜を形成させることを特徴とす
る、粒径0.05μｍ〜0.5mmの蓄熱材封入マイクロカプセ
ルの製造法。1. A water-soluble surfactant aqueous solution prepared by dispersing a heat storage material as an emulsion or suspension in a monomer containing an oil-soluble surfactant and inactive to an inorganic hydrate heat storage material. Dropping in, then polymerizing the monomer covering the surface of the heat storage material in a dispersed state in the aqueous solution in the presence of a polymerization initiator, to form a capsule film, particle size 0.05 Manufacturing method of microcapsules containing heat storage material of μm to 0.5 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61253156A JPH0640952B2 (en) | 1985-11-29 | 1986-10-24 | Manufacturing method of microcapsule containing heat storage material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-267392 | 1985-11-29 | ||
| JP26739285 | 1985-11-29 | ||
| JP61253156A JPH0640952B2 (en) | 1985-11-29 | 1986-10-24 | Manufacturing method of microcapsule containing heat storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62225241A JPS62225241A (en) | 1987-10-03 |
| JPH0640952B2 true JPH0640952B2 (en) | 1994-06-01 |
Family
ID=26541059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61253156A Expired - Lifetime JPH0640952B2 (en) | 1985-11-29 | 1986-10-24 | Manufacturing method of microcapsule containing heat storage material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0640952B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6241909B1 (en) * | 1995-09-07 | 2001-06-05 | Claude Q. C. Hayes | Heat absorbing temperature control devices and method |
| KR100481283B1 (en) * | 2001-08-27 | 2005-04-07 | 주식회사 에네트 | Microencapsulation Method of Phase Change Materials(PCM) using Emulsion |
| JP5505919B2 (en) * | 2006-10-26 | 2014-05-28 | 日産自動車株式会社 | Manufacturing method of heat storage material microcapsule and heat storage material microcapsule |
| JP2012140600A (en) | 2010-12-13 | 2012-07-26 | Konica Minolta Business Technologies Inc | Heat storage microcapsule and method for manufacturing the same |
| CN104937066A (en) * | 2013-01-10 | 2015-09-23 | 吉坤日矿日石能源株式会社 | Microencapsulated heat storage material, method of manufacture and use thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5841559B2 (en) * | 1977-06-22 | 1983-09-13 | 株式会社リコー | Operation confirmation method for power generation telemeter |
| JPS5442380A (en) * | 1978-08-15 | 1979-04-04 | Matsushita Electric Works Ltd | Regenerative capsule |
| JPS56142398A (en) * | 1980-04-03 | 1981-11-06 | Agency Of Ind Science & Technol | Material and method for accumulating heat by using substance capable of undergoing phase change |
| JPS60824A (en) * | 1983-06-20 | 1985-01-05 | Pola Chem Ind Inc | Manufacture of microcapsule |
-
1986
- 1986-10-24 JP JP61253156A patent/JPH0640952B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 近藤保、小石真純「マイクロカプセル−その製法・性質・応用」Ｐ．３５〜４２（昭５３−１１−２５）三共出版 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62225241A (en) | 1987-10-03 |
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