JPH01247478A - Polyethylene oxide heat storage material - Google Patents
Polyethylene oxide heat storage materialInfo
- Publication number
- JPH01247478A JPH01247478A JP63075704A JP7570488A JPH01247478A JP H01247478 A JPH01247478 A JP H01247478A JP 63075704 A JP63075704 A JP 63075704A JP 7570488 A JP7570488 A JP 7570488A JP H01247478 A JPH01247478 A JP H01247478A
- Authority
- JP
- Japan
- Prior art keywords
- heat storage
- polyethylene oxide
- storage material
- heat
- added
- 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.)
- Granted
Links
- 238000005338 heat storage Methods 0.000 title claims abstract description 51
- 229920003171 Poly (ethylene oxide) Polymers 0.000 title claims abstract description 46
- 239000011232 storage material Substances 0.000 title claims abstract description 31
- -1 polypropylene Polymers 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 239000002667 nucleating agent Substances 0.000 claims description 22
- 239000002516 radical scavenger Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 abstract description 7
- 238000004781 supercooling Methods 0.000 abstract description 7
- 239000004793 Polystyrene Substances 0.000 abstract description 4
- 229920002223 polystyrene Polymers 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002292 Nylon 6 Polymers 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 239000000344 soap Substances 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 9
- 230000004927 fusion Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 241000172160 Caloria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000008016 pharmaceutical coating Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規なポリエチレンオキシド蓄熱材に関するも
のである。さらに詳しくいえば、本発明は、蓄熱密度が
大きく、過冷却や相分離現象を起こすことなく安定な動
作が可能で、かつ耐久性に優れる上に、比較的広い温度
範囲に適用しうる、ポリエチレンオキシドの相転移に伴
う熱の吸収・放出を利用した潜熱利用型の安価なポリエ
チレンオキシド蓄熱材に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel polyethylene oxide heat storage material. More specifically, the present invention is a polyester resin that has a large heat storage density, can operate stably without causing supercooling or phase separation, is highly durable, and can be applied over a relatively wide temperature range. This invention relates to an inexpensive latent heat-utilizing polyethylene oxide heat storage material that utilizes the absorption and release of heat associated with the phase transition of ethylene oxide.
従来の技術
「蓄熱」は、太陽熱や工場廃熱など、その発生量と発生
時間が不安定な熱エネルギーを一時的に貯蔵することに
よって、任意の時間に任意の量の黙エネルギーを利用で
きるようにするための技術であり、石油シｄツクを契機
として積極的に研究が行われている。この蓄熱の方法と
しては、物質の頭熱を利用する方法と、物質の相変化に
伴う潜熱を利用する方法とが知られている。前者の顕然
を利用する方法においては、蓄熱材として、通常水や岩
石のように単位体積当りの熱容量の大きな物質が用いら
れるが、該蓄熱材は単位体積当りの蓄熱密度が小さいた
めに、蓄熱槽が極めて大きなものになるのを免れないと
いう欠点がある。The conventional technology "thermal storage" is a method that allows you to use any amount of silent energy at any time by temporarily storing thermal energy whose generation amount and time are unstable, such as solar heat and factory waste heat. This technology is being actively researched in the wake of oil shocks. As methods for storing heat, there are two known methods: one that utilizes the head heat of a substance, and the other that utilizes latent heat that accompanies a phase change of the substance. In the former method, a substance with a large heat capacity per unit volume, such as water or rock, is usually used as the heat storage material, but since the heat storage material has a low heat storage density per unit volume, The drawback is that the heat storage tank is inevitably extremely large.
これに対し、後者の相変化に伴う潜熱を利用する方法は
、通常蓄熱材として、無機水利塩などを用い、主にその
溶融／凝固の際の溶融潜熱を利用するもので、蓄熱槽を
小型化しうるという利点を有している。しかしながら、
該無機水利塩は、過冷却や相分離現象を起こすため、熱
の入山がうまくいかず、蓄熱材として長期間安定な動作
を行わせることが困難であるという欠点を有している。On the other hand, the latter method, which utilizes latent heat associated with phase change, usually uses inorganic water salt as the heat storage material, and mainly utilizes the latent heat of fusion during melting/solidification, making the heat storage tank compact. It has the advantage of being configurable. however,
The inorganic water salt has the disadvantage that it causes supercooling and phase separation phenomena, and therefore does not allow heat to enter the water well, making it difficult to operate stably for a long period of time as a heat storage material.
また、この相変化に伴う潜熱を利用する方法においては
、蓄熱材の融点が熱の使用目的温度近傍になければなら
ないため、蓄熱材として利用しうる物質が限られていＩ
；。In addition, in the method of utilizing the latent heat accompanying this phase change, the melting point of the heat storage material must be close to the intended use temperature of the heat, so the materials that can be used as the heat storage material are limited.
;.
ところで、ポリエチレンオキシドは、和紙抄紙用や、糊
、接着剤、界面活性剤、医薬品コーティング用などとし
て広く用いられており、このものを前記潜熱利用型蓄熱
材として用いる場合、（１）分子量によって融解温度を
制御しうるので、分子量を選択することによって適用温
度を決めることができる、（２）相分離現象を起こさな
い、（３）大量生産されており、安価で安全性が高い、
など多くの利点を有している。しかしながら、このポリ
エチレンオキシドは、無機水利塩はどではないが、過冷
却を起こしやすく、かつ高温で用いる場合、加熱−冷却
の繰り返しによって、短期間で劣化し、蓄熱能力が失わ
れるという欠点を有している。By the way, polyethylene oxide is widely used for Japanese paper making, pastes, adhesives, surfactants, pharmaceutical coatings, etc. When using this material as the latent heat utilization type heat storage material, (1) It melts depending on the molecular weight. Since the temperature can be controlled, the applicable temperature can be determined by selecting the molecular weight; (2) it does not cause phase separation; (3) it is mass-produced, inexpensive and highly safe;
It has many advantages such as However, although this polyethylene oxide is not an inorganic water salt, it is prone to supercooling, and when used at high temperatures, it deteriorates in a short period of time due to repeated heating and cooling, resulting in a loss of heat storage capacity. are doing.
発明が解決しようとする課題
本発明は、このような事情に鑑み、蓄熱密度が大きく、
過冷却や相分離現象を起こすことなく安定な動作が可能
で、かつ耐久性に優れる上に、比較的広い温度範囲に適
用しうる安価な蓄熱材を提供することを目的としてなさ
れたものである。Problems to be Solved by the Invention In view of these circumstances, the present invention has a high heat storage density,
The purpose was to provide an inexpensive heat storage material that can operate stably without overcooling or phase separation, has excellent durability, and can be applied over a relatively wide temperature range. .
課題を解決するための手段
本発明者らは、ポリエチレンオキシドが有する前記の利
点に着目し、このポリエチレンオキシドを用いて前記の
好ましい性質を有する蓄熱材を開発するために鋭意研究
を重ねた結果、該ポリエチレンオキシドに核剤を加える
ことにより、その過冷却が抑制されて、球晶の数が増大
し、かつ球晶が微細化され、結晶化速度が速くなる上、
結晶化度も増大して蓄熱密度が大きくなること、このよ
うな効果は蓄熱材を大量に用いる場合に特に顕著である
こと、さらに、ラジカル捕捉剤を添加することにより、
高温での加熱−冷却の繰り返しによって発生するラジカ
ルが安定化され、ポリエチレンオキシドの劣化が抑制さ
れることなどを見出し、この知見に基づいて本発明を完
成するに至った。Means for Solving the Problems The present inventors focused on the above-mentioned advantages of polyethylene oxide, and as a result of intensive research to develop a heat storage material having the above-mentioned preferable properties using this polyethylene oxide, By adding a nucleating agent to the polyethylene oxide, its supercooling is suppressed, the number of spherulites is increased, the spherulites are made finer, and the crystallization rate is increased,
The degree of crystallinity also increases and the heat storage density increases, and this effect is particularly noticeable when a large amount of heat storage material is used.Furthermore, by adding a radical scavenger,
It was discovered that the radicals generated by repeated heating and cooling at high temperatures are stabilized and deterioration of polyethylene oxide is suppressed, and the present invention was completed based on this knowledge.
すなわち、本発明は、（Ａ）ポリエチレンオキシドに、
（Ｂ）核剤を含有させた組成物から成るポリエチレンオ
キシド蓄熱材、及び前記組成物に、さらに（Ｃ）成分と
してラジカル捕捉剤を含有させた組成物から成るポリエ
チレンオキシド蓄熱材を提供するものである。That is, the present invention provides (A) polyethylene oxide,
(B) A polyethylene oxide heat storage material made of a composition containing a nucleating agent, and a polyethylene oxide heat storage material made of a composition further containing a radical scavenger as a component (C). be.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明蓄熱材に用いられる組成物の（Ａ）成分であるポ
リエチレンオキシドとしては、使用目的温度に応じて種
々の分子量（融解温度）のものを使用することができ、
またその形状については塊状、粒状、板状、粉末状、液
状など、いずれの形状のものであってもよいし、ハイサ
ーム、サームエス、カロリア、シリコンオイルなどの各
種の熱媒体と混ぜてスラリー状としたものであってもよ
く、あるいはγ線などの電離放射線を照射してポリエチ
゛レンオキシドの分子間を架橋し、所望形状に成形し
たものであってもよい。As the polyethylene oxide which is the component (A) of the composition used in the heat storage material of the present invention, polyethylene oxide having various molecular weights (melting temperature) can be used depending on the intended use temperature.
In addition, it can be in any shape such as lump, granule, plate, powder, or liquid, or it can be mixed with various heat media such as Hytherm, Therm-S, Caloria, and silicone oil to form a slurry. Alternatively, the polyethylene oxide molecules may be crosslinked by irradiation with ionizing radiation such as gamma rays, and formed into a desired shape.
該ｌｌｌ１ｔ物にＣＢ）成分として用いられる核剤とし
ては、例えばアタクチックポリスチレン、イソタクチッ
クポリスチレン、インタクチツクポリプロピレン、ポリ
エチレン、１．４−）ランスポリブタジェン、ナイロン
６、ナイロン６６、ナイロンｇｏ＋、ポリエチレンテレ
フタレート、ポリオキシメチレンなどの、前記（Ａ）成
分として使用するポリエチレンオキシドよりも融点の高
いポリマー及びそれらの共重合体、アルミナなどの金属
酸化物、シリカなどの非金属酸化物、金属セッケンなど
の金属塩などを挙げる二きができる。これらの核剤はｌ
積用いてもよいし、２種以上組み合わせて」いてもよく
、また前記アルミナやシリカなどは、表面をシランなと
で修飾したものであってもよい。これらの核剤の添加量
はごく微量でよ＜、（Ａ）成分のポリエチレンオキシド
に対して、通常０．０００１〜Ｏ９１重量％の割合で添
加される。Examples of the nucleating agent used as the CB) component in the product include atactic polystyrene, isotactic polystyrene, intact polypropylene, polyethylene, 1.4-)transpolybutadiene, nylon 6, nylon 66, and nylon go+. , polyethylene terephthalate, polyoxymethylene, and other polymers with a higher melting point than the polyethylene oxide used as component (A) and their copolymers, metal oxides such as alumina, nonmetal oxides such as silica, metal soaps. There are two examples of metal salts such as. These nucleating agents are l
They may be used in combination or in combination of two or more, and the surface of the alumina, silica, etc. may be modified with silane or the like. The amount of these nucleating agents added is very small, and is usually added in a proportion of 0.0001 to 91% by weight based on the polyethylene oxide of component (A).
本発明蓄熱材は、低温で使用する場合には劣化がほとん
ど生じないが、高温で使用する場合や、該ポリエチレン
オキシドが製造時の触媒などの金属化合物残渣を含んで
いる場合には、劣化が生じやすいために、さらに（Ｃ）
成分としてラジカル捕捉剤を添加することが望ましい。The heat storage material of the present invention hardly deteriorates when used at low temperatures, but when used at high temperatures or when the polyethylene oxide contains metal compound residues such as catalysts during production, deterioration occurs. In addition, (C)
It is desirable to add a radical scavenger as a component.
このラジカル捕捉剤としては、例えばフェノール、クレ
ゾール、ヒドロキノン、カテコール、アニソール、キシ
レノール、２．２′−メチレンビス（６−ｔ−ブチル−
ｐ−クレゾール）、２．６−ジーｔ−ブチル−ｐ−クレ
ゾールなどのフェノール化合物、トニトロソアニリン、
トニトロソアミン、フェニレンジアミン、φ
エチレンジアミン、Ｎ−フェニル−Ｎ′−クロヘキシル
−ｐ−７二二レンジアミンなどのアミン化合物などが挙
げられる。これらのラジカル捕捉剤は１種用いてもよい
し、２種以上を組み合わせて用いてもよく、゛またその
添加量は（Ａ）成分のポリエチレンオキシドに対し、通
常０．１〜１重量％の範囲で選ばれるが、蓄熱材の使用
期間が長い場合や、該ポリエチレンオキシドが金属化合
物残渣を多量に含有している場合などでは、該ラジカル
捕捉剤の添加量を増やすことが望ましい。Examples of the radical scavenger include phenol, cresol, hydroquinone, catechol, anisole, xylenol, 2,2'-methylenebis(6-t-butyl-
p-cresol), phenolic compounds such as 2,6-di-t-butyl-p-cresol, tonitrosoaniline,
Examples include amine compounds such as tonitrosamine, phenylenediamine, φ ethylenediamine, and N-phenyl-N'-chlorohexyl-p-7 22-diamine. These radical scavengers may be used alone or in combination of two or more, and the amount added is usually 0.1 to 1% by weight based on the polyethylene oxide of component (A). Although it is selected within a range, it is desirable to increase the amount of the radical scavenger added when the heat storage material is used for a long time or when the polyethylene oxide contains a large amount of metal compound residue.
ポリエチレンオキシドに核剤を添加する場合には、融解
させたポリエチレンオキシドに、核剤の微粉末を加え、
かきまぜて毘合するなどして均一に分散させることが望
ましい。また、ラジカル捕捉剤を添加する場合は、劣化
がポリエチレンオキシドの表面から進行するために、そ
の表面に塗布したり、融解させたポリエチレンオキシド
の表面にラジカル捕捉剤の粉末を付着させたり、あるい
はラジカル捕捉剤を高濃度に分散したポリエチレンオキ
シドを表層とするなどして、ラジカル捕捉剤の濃度が蓄
熱材の表面で高くなるようにすることが望ましい。When adding a nucleating agent to polyethylene oxide, add fine powder of the nucleating agent to the melted polyethylene oxide,
It is desirable to uniformly disperse the mixture by stirring and mixing. In addition, when adding a radical scavenger, deterioration progresses from the surface of polyethylene oxide, so it is necessary to apply it to the surface, attach radical scavenger powder to the surface of melted polyethylene oxide, or remove radicals. It is desirable that the concentration of the radical scavenger be increased on the surface of the heat storage material, such as by forming the surface layer of polyethylene oxide in which the scavenger is dispersed at a high concentration.
また、本発明蓄熱材に用いられる組成物には、熱伝導度
や熱の入出力速度を大きくするために、所望に応じ金属
粉、金属繊維、炭素粉、炭素繊維などを添加してもよい
。Further, metal powder, metal fiber, carbon powder, carbon fiber, etc. may be added to the composition used for the heat storage material of the present invention as desired in order to increase thermal conductivity and heat input/output rate. .
発明の効果
本発明のポリエチレンオキシド蓄熱材は、ポリエチレン
オキシドに核剤又は核剤とラジカル捕捉剤とを含有させ
た組成物から成るものであって、蓄熱密度が大きく、過
冷却や相分離現象を起こすことがない上、耐久性に優れ
ていて長期間の使用に際しても蓄熱能力が低下しないの
で、安定な動作が可能であり、しかも分子量を適当に選
ぶことによって、比較的広い範囲の温度に適用しうるな
と、擾れた特徴を有することから、例えば太陽エネルギ
ーや工場廃熱などの熱エネルギーの回収、利用に好適に
用いられる。Effects of the Invention The polyethylene oxide heat storage material of the present invention is composed of a composition in which polyethylene oxide contains a nucleating agent or a nucleating agent and a radical scavenger, has a high heat storage density, and is resistant to supercooling and phase separation phenomena. In addition, it has excellent durability and does not lose its heat storage capacity even when used for a long period of time, so it can operate stably. Furthermore, by appropriately selecting the molecular weight, it can be used over a relatively wide range of temperatures. Due to its unique characteristics, it is suitable for recovering and utilizing thermal energy such as solar energy and factory waste heat.
実施例
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によつてなんら限定されるものでは
ない。Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited to these examples in any way.
実施例！
分子量＋６（１０のポリエチレンオキシド１＆ｇに核剤
としてインタクチツクポリスチレンの微粉末０．７゜を
加え加熱しながらかきまぜ、良く分散させた。Example! 0.7° fine powder of intact polystyrene was added as a nucleating agent to 1&g of polyethylene oxide having a molecular weight of +6 (10) and stirred while heating to disperse well.
これを蓄熱槽に移し、シリコーン油を熱媒体として用い
て蓄熱及び放熱を行い、冷却曲線とポリエチレンオキシ
ドの融解熱による潜熱蓄熱量を測定した。その結果、冷
却曲線で現われるプラトー、つまり見かけの凝固点は、
核剤を添加しない場合に比べ９℃上昇し、２９℃となっ
Ｉ；。また、蓄熱量も核剤を添加しない場合に比べ、９
％増加し、３９＆ｃｉｌとなつＩ；。This was transferred to a heat storage tank, and silicone oil was used as a heat medium to store and release heat, and the cooling curve and the amount of latent heat stored due to the heat of fusion of polyethylene oxide were measured. As a result, the plateau, or apparent freezing point, that appears in the cooling curve is
Compared to the case where no nucleating agent was added, the temperature increased by 9°C to 29°C. In addition, the amount of heat storage is also 9% higher than when no nucleating agent is added.
% increase to 39&cil;.
実施例２
分子［６００のポリエチレンオキシドＬｋｇに核剤とし
てポリエチレンテレフタレートの微粉末０．８ｇを加え
、実施例１と同様にして冷却曲線と放！ＩＡｎを測定し
た。その結果、核剤を添加しない場合に比べ、見かけの
凝固点が８℃上昇して１０℃となり、蓄熱量も３２＆ｃ
！ｌと１０％増加した。Example 2 0.8 g of fine powder of polyethylene terephthalate was added as a nucleating agent to 600 L kg of polyethylene oxide molecules, and the cooling curve and release curve were measured in the same manner as in Example 1. IAn was measured. As a result, the apparent freezing point rose by 8°C to 10°C compared to when no nucleating agent was added, and the amount of heat storage also increased by 32°C.
! l and increased by 10%.
実施例３
分子量５２０のポリエチレンオキシド１＆９に核剤とし
てナイロン６６の微粉末１．０ｇを加え、実施例１と同
様にして冷却曲線と放熱量を測定した。Example 3 1.0 g of fine powder of nylon 66 was added as a nucleating agent to polyethylene oxide 1 & 9 having a molecular weight of 520, and the cooling curve and heat release amount were measured in the same manner as in Example 1.
その結果、核剤を添加しない場合に比べ、見かけの凝固
点が６℃上昇して３℃となり、蓄熱量も２６＆ｃ＊Ｉと
１２％増加した。As a result, compared to the case where no nucleating agent was added, the apparent freezing point increased by 6°C to 3°C, and the amount of heat storage increased by 12% to 26&c*I.
実施例４
分子量！００８０のポリエチレンオキシド１ｋｇに核剤
としてシリカ０．９ｇを加え、実施例１と同様にして冷
却曲線と蓄熱量を測定した。その結果、核剤を添加しな
い場合に比べ、見かけの凝固点が９℃上昇して４７℃と
なり、蓄熱量も４３ｋｃａｌと１０％増加した。Example 4 Molecular weight! 0.9 g of silica was added as a nucleating agent to 1 kg of polyethylene oxide No. 0080, and the cooling curve and heat storage amount were measured in the same manner as in Example 1. As a result, compared to the case where no nucleating agent was added, the apparent freezing point increased by 9° C. to 47° C., and the amount of heat storage also increased by 10% to 43 kcal.
実施例５
分子量約＋５ａｏｏｏのポリエチレンオキシド１ｋｇに
表面を酸化させたアルミニウムの微粉末１．０９を加え
、実施例１と同様にして冷却曲線と蓄熱量を測定した。Example 5 1.09 kg of aluminum fine powder with an oxidized surface was added to 1 kg of polyethylene oxide having a molecular weight of approximately +5 aooo, and the cooling curve and heat storage amount were measured in the same manner as in Example 1.
その結果、見かけの凝固温度が９℃上昇して４８℃とな
り、蓄熱量も４２ｋｃａｌと１２％増加しＩ；。As a result, the apparent solidification temperature increased by 9 degrees Celsius to 48 degrees Celsius, and the amount of heat storage increased by 12% to 42 kcal.
実施例１で用いたのと同様のポリエチレンオキシド蓄熱
材３ｇをとり、これに、ラジカル捕捉剤として！、２゛
−メチレンビス（６−ｔ−ブチル−ｐ−クレゾール）３
０履９（１！１！量％）を加えて混合したのち、試験管
に入れ、２０℃から６時間かけて１５０℃に上げ、その
温度に８時間保持し、その後、５時間かけて２０℃まで
冷却するという１日１回の２０℃〜１５０℃の加熱冷却
サイクルを２カ月間繰り返した。このようにして空気雰
囲気中で２力月間の蓄熱−放熱実験を行った試料の融解
熱量を示差走査熱量計で測定した結果、ラジカル捕捉剤
を添加しない場合篇には融解熱量が０になってしまった
が、ラジカル捕捉剤を添加した場合には融解熱量の低下
がほとんど見られなかった。Take 3 g of polyethylene oxide heat storage material similar to that used in Example 1, and use it as a radical scavenger! , 2'-methylenebis(6-t-butyl-p-cresol)3
After adding and mixing 0 to 9 (1!1!% by volume), put it in a test tube, raise it from 20 °C to 150 °C over 6 hours, keep at that temperature for 8 hours, and then add 20 °C over 5 hours. A heating/cooling cycle of 20°C to 150°C once a day was repeated for 2 months. As a result of measuring the heat of fusion using a differential scanning calorimeter of the sample subjected to heat storage and heat release experiments for 2 months in an air atmosphere, the heat of fusion was 0 in the case where no radical scavenger was added. However, when a radical scavenger was added, there was almost no decrease in the heat of fusion.
実施例７
実施例４で用いたのと同様のポリエチレンオキシド蓄熱
材３ｖをとり、これに、ラジカル捕捉剤として２．６−
ジー１−・ブチル−ｐ−クレゾール３０１１ｇ（１重量
％）を加えて、実施例６と同様の蓄熱−放熱実験を２カ
月間行った。その結果、ラジカル捕捉剤を添加しない場
合には融解熱量が０になってしまったが、ラジカル捕捉
剤を添加した場合には融解熱量の低下がほとんど見られ
なかった。Example 7 3V of polyethylene oxide heat storage material similar to that used in Example 4 was taken, and 2.6-
3011 g (1% by weight) of di-1-butyl-p-cresol was added, and a heat storage-heat release experiment similar to that in Example 6 was conducted for two months. As a result, when no radical scavenger was added, the heat of fusion became 0, but when a radical scavenger was added, there was almost no decrease in the heat of fusion.
実施例８
実施例５で用いたのと同様のポリエチレンオキシド蓄熱
材３ｇをとり、これに、ラジカル捕捉剤としてＮ−フェ
ニル−Ｎ′−シクロへキシル−ｐ−７二二レンジアミン
ａｏ＊ｙ（２重量％）を加えて、実施例６と同様の蓄熱
−放熱実験を１カ月間行った。Example 8 3 g of polyethylene oxide heat storage material similar to that used in Example 5 was taken, and N-phenyl-N'-cyclohexyl-p-7 2-2-diamine ao*y ( 2% by weight), and a heat storage-heat radiation experiment similar to that in Example 6 was conducted for one month.
その結果、ラジカル捕捉剤を添加しなかった場合には融
解熱量が０になってしまったが、ラジカル捕捉剤を添加
した場合には融解熱量の低下がほとんど見られなかった
。As a result, when no radical scavenger was added, the heat of fusion became 0, but when a radical scavenger was added, there was almost no decrease in the heat of fusion.
特許出願人 工業技術院長 飯 塚 幸 三指定代理人
工業技術院名古屋工業技術試験所長磯谷三男Patent applicant: Yukio Iizuka, Director of the Agency of Industrial Science and Technology Designated agent: Mitsuo Isotani, Director of the Nagoya Industrial Technology Testing Institute, Agency of Industrial Science and Technology
Claims (1)
させた組成物から成るポリエチレンオキシド蓄熱材。 ２ 核剤が、（Ａ）成分のポリエチレンオキシドよりも
高い融点を有するポリマー、金属酸化物、非金属酸化物
及び金属塩の中から選ばれた少なくとも１種である請求
項１記載の蓄熱材。 ３ （Ａ）ポリエチレンオキシドに、（Ｂ）核剤及び（
Ｃ）ラジカル捕捉剤を含有させた組成物から成るポリエ
チレンオキシド蓄熱材。 ４ 核剤が、（Ａ）成分のポリエチレンオキシドよりも
高い融点を有するポリマー、金属酸化物、非金属酸化物
及び金属塩の中から選ばれた少なくとも１種である請求
項３記載の蓄熱材。 ５ ラジカル捕捉剤がフェノール化合物及びアミン化合
物の中から選ばれた少なくとも１種である請求項３又は
４記載の蓄熱材。[Claims] 1. A polyethylene oxide heat storage material comprising a composition containing (A) polyethylene oxide and (B) a nucleating agent. 2. The heat storage material according to claim 1, wherein the nucleating agent is at least one selected from polymers, metal oxides, non-metal oxides, and metal salts having a higher melting point than the polyethylene oxide of component (A). 3 (A) polyethylene oxide, (B) nucleating agent and (
C) A polyethylene oxide heat storage material comprising a composition containing a radical scavenger. 4. The heat storage material according to claim 3, wherein the nucleating agent is at least one selected from polymers, metal oxides, nonmetal oxides, and metal salts having a higher melting point than the polyethylene oxide of component (A). 5. The heat storage material according to claim 3 or 4, wherein the radical scavenger is at least one selected from phenolic compounds and amine compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63075704A JPH01247478A (en) | 1988-03-29 | 1988-03-29 | Polyethylene oxide heat storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63075704A JPH01247478A (en) | 1988-03-29 | 1988-03-29 | Polyethylene oxide heat storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01247478A true JPH01247478A (en) | 1989-10-03 |
| JPH0471954B2 JPH0471954B2 (en) | 1992-11-17 |
Family
ID=13583874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63075704A Granted JPH01247478A (en) | 1988-03-29 | 1988-03-29 | Polyethylene oxide heat storage material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01247478A (en) |
-
1988
- 1988-03-29 JP JP63075704A patent/JPH01247478A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0471954B2 (en) | 1992-11-17 |
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