JPS62250940A - Temperature responsive porous gel and its preparation - Google Patents
Temperature responsive porous gel and its preparationInfo
- Publication number
- JPS62250940A JPS62250940A JP9383286A JP9383286A JPS62250940A JP S62250940 A JPS62250940 A JP S62250940A JP 9383286 A JP9383286 A JP 9383286A JP 9383286 A JP9383286 A JP 9383286A JP S62250940 A JPS62250940 A JP S62250940A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- methyl ether
- polyvinyl methyl
- gel
- water
- 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
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000010894 electron beam technology Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 230000007704 transition Effects 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 229920001289 polyvinyl ether Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000005191 phase separation Methods 0.000 abstract 2
- 238000004062 sedimentation Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000004043 responsiveness Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
Landscapes
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、水の存在下において、温度により可逆的に形
態変化しつる温度応答性多孔質ゲル、及びその製造方法
に関するものである。さらに詳しくいえば、本発明は、
メカノケミカル材料として。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a temperature-responsive porous gel that reversibly changes shape depending on temperature in the presence of water, and a method for producing the same. More specifically, the present invention
As a mechanochemical material.
例えばエネルギー変換、エネルギー貯蔵、アクチェータ
ー、センサー、吸脱木材、放水剤、玩具などへの利用が
可能な、水の存在下において低温で膨潤を高温で収縮を
可逆的に繰り返しうるポリビニルエーテルの架橋ゲルか
ら成る温度応答性に優几た多孔質ゲル、及びこのものを
効果的に製造する方法に関するものである。For example, cross-linked polyvinyl ether gel that can be used for energy conversion, energy storage, actuators, sensors, absorbent wood, water release agents, toys, etc., and can reversibly swell at low temperatures and contract at high temperatures in the presence of water. The present invention relates to a porous gel with excellent temperature responsiveness, and a method for effectively producing the gel.
従来の技術 従来、温度により形態が変化する材料としては。Conventional technology Conventionally, materials that change shape depending on temperature include:
無機材料では形状記憶合金が知ら汎ており、このものは
、種々の分野で利用さ１はじめている。−万、有機材料
においては、ポリメタクリル酸ゲルがポリエチレングリ
コール水溶液中で温度全変化させることにより、可逆的
に伸縮することが知ら几ている〔「ジャーナル・オプ・
ポリマー・サイエンス（Ｊ、 Ｐｏｌｙｍｅｒ Ｓｃｉ
、 ） Ｊ第１５巻、第２５５ページ（１９７７年）〕
。さらにポリアクリルアミドゲルが水−アセトン系にお
いて、温度を上昇させることにより膨潤し、下げること
により収縮することが報告さｎてお９〔「フィジカル・
レビュー・レターズ（Ｐｈｙｓｉｃａｌ Ｒｅｖｉｅｗ
Ｌｅｔｔｅ−１日）」第４０巻、第８２０ページ（１
９７８年）〕、また、この報告において、このような現
象の利用の可能性として、化学エンジン、人工筋肉、化
学パルプ、エネルギー変換、エネルギー貯ｔ センサー
などへの応用が挙げらｎている。Shape memory alloys are widely known among inorganic materials, and are beginning to be used in various fields. - Among organic materials, it is known that polymethacrylic acid gel reversibly expands and contracts by completely changing the temperature in an aqueous polyethylene glycol solution [Journal Op.
Polymer Science (J, Polymer Sci
, ) J Volume 15, Page 255 (1977)]
. Furthermore, it has been reported that polyacrylamide gel swells when the temperature is raised and contracts when the temperature is lowered in a water-acetone system.
Review Letters (Physical Review Letters)
Volume 40, page 820 (1 day)
978)], this report also mentions possible uses of this phenomenon, including applications to chemical engines, artificial muscles, chemical pulp, energy conversion, energy storage sensors, etc.
しかしながら、こ几らの温度応答性五機材料においては
、いずｎもゲル状を呈しておシ、材料が温度により膨潤
、収縮する場合には、ゲルを構成している液体の吸収や
放出が伴い、この液体のゲル中の拡散が該材料の温度応
答性の律速となるため、応答性の良い材料を得るには、
ゲルの直径全車さくしたり、細い繊維状のゲルを調製す
ることが必要であるが、材料の強度の面がらまだ解決さ
１ておらず、したがって、温度応答性に劣るという欠点
を有している。However, all of these temperature-responsive five-layer materials exhibit a gel-like appearance, and when the material swells or contracts due to temperature, it absorbs or releases the liquid that makes up the gel. , and the diffusion of this liquid in the gel is the rate-determining factor for the temperature responsiveness of the material, so in order to obtain a material with good responsiveness,
It is necessary to reduce the entire diameter of the gel or to prepare a thin fibrous gel, but the strength of the material has not yet been resolved and therefore has the disadvantage of poor temperature response. .
発明が解決しようとする問題点
本発明の目的は、このような事情のもとで、水の存在下
において、温度により可逆的に形態変化しうる温度応答
性に優ｎたＭ機材料を提供することにある。Problems to be Solved by the Invention Under these circumstances, an object of the present invention is to provide an M-type material with excellent temperature responsiveness that can reversibly change its shape depending on temperature in the presence of water. It's about doing.
ところで、ポリビニルメチルエーテルは、低温では水素
結合により水が水和して水溶性であるが、相転移温度（
３２〜４０℃）以上の温度では水素結合が破壊さｆ′Ｌ
、脱水和を起こして水に不溶化することが知られている
。このような現象は転移温度を境にして可逆的でちり、
系の温度を転移点より低くすれば再度水和が起こって水
に溶解する。By the way, polyvinyl methyl ether is water-soluble at low temperatures due to hydration due to hydrogen bonding, but at low temperatures it becomes water-soluble.
At temperatures above 32-40℃, hydrogen bonds are broken f'L
is known to cause dehydration and become insoluble in water. This phenomenon is reversible beyond the transition temperature, and
If the temperature of the system is lowered below the transition point, hydration occurs again and it dissolves in water.
本発明者らは、先に、このポリビニルメチルエーテルの
親水性及び疎水性の温度による可逆的な変化を利用して
、水中の疎水性万機物質を吸着分離する方法を提案した
が（特公昭６１−２４０３号公報）、さらに研究を重ね
た結果、ポリビニルメチルエーテルの架橋ゲルが、水中
において温度により可逆的に膨潤、収縮することを見出
した。The present inventors previously proposed a method for adsorbing and separating hydrophobic substances in water by utilizing the reversible temperature-dependent changes in the hydrophilicity and hydrophobicity of polyvinyl methyl ether (Tokuko Showa). 61-2403), and as a result of further research, it was discovered that a crosslinked gel of polyvinyl methyl ether reversibly swells and contracts in water depending on the temperature.
しかしながら、このようなゲルの温度変化による膨潤、
収縮の速度はゲル中の水の拡散速度に依存するために、
前記ポリビニルメチルエーテルの架橋ゲルにおいては、
膨潤、収縮平衡に達するのに、数時間から数日間を要し
、温度応答性が著しく低い。この点を改良するには細い
繊維状のゲルや、微細なゲルを作成し、水の拡散距離を
短くすることも考えら几るが、ゲルの使用目的によって
は、こ几らの方法は必ずしも適しているとはいえない。However, swelling due to temperature changes of such gels,
Since the rate of shrinkage depends on the rate of diffusion of water in the gel,
In the crosslinked gel of polyvinyl methyl ether,
It takes several hours to several days to reach swelling and contraction equilibrium, and the temperature response is extremely low. To improve this point, it is possible to create thin fibrous gels or fine gels to shorten the water diffusion distance, but depending on the purpose of the gel, these methods are not always possible. It cannot be said that it is suitable.
問題点を解決するための手段
本発明者らは鋭意研究を重ねた結果、ポリビニルメチル
エーテル水溶液が温度により相転移を起こすことに着目
し、所定濃度のポリビニルメチルエーテル水溶液を該ポ
リビニルメチルエーテルの相転移温度付近の温度に維持
して、ガンマ線又は電子線を照射することにより、ポリ
ビニルエーテルの架橋ゲルから成る微細な空孔を有する
多孔質ゲルが得らｎ、前記目的を達成しうることを見出
し、この知見に基づいて本発明を完成するに至っ念。Means for Solving the Problems As a result of extensive research, the present inventors focused on the fact that a polyvinyl methyl ether aqueous solution undergoes a phase transition depending on temperature. It has been found that by maintaining the temperature near the transition temperature and irradiating with gamma rays or electron beams, a porous gel having fine pores made of a crosslinked polyvinyl ether gel can be obtained, and the above object can be achieved. Based on this knowledge, we were determined to complete the present invention.
すなわち１本発明は、微細な空孔を有するポリビニルエ
ーテルの架橋ゲルから成り、かつ水の存在下において、
温度により可逆的に形態変化しうる温度応答性多孔質ゲ
ルを提供するものであり。That is, 1 the present invention consists of a crosslinked gel of polyvinyl ether having fine pores, and in the presence of water,
The present invention provides a temperature-responsive porous gel that can reversibly change its shape depending on temperature.
このものは、ポリビニルメチルエーテル５〜５０重量％
全含有する水溶液を所要形状に保ち、その温度を該ポリ
ビニルメチルエーテルの相転移温度付近に維持して、ガ
ンマ線又は電子線を照射することによって製造すること
ができる。This stuff is polyvinyl methyl ether 5-50% by weight
It can be produced by irradiating the polyvinyl methyl ether with gamma rays or electron beams while keeping the aqueous solution containing the whole in the desired shape and maintaining its temperature around the phase transition temperature of the polyvinyl methyl ether.
本発明において用いるポリビニルメチルエーテルは、通
常、ビニルメチルエーテルを、例えばＢＦ３． 工２
、ＡｔＣ１ｔ、 、 ＦｅＣ４５などを開始剤としてカ
チオン重合させることによって得ら江る。このものは、
水の存在下において、相転移温度より低い温度では、水
素結合により水が水和して水溶性となり、″１之相転移
温度以上の温度では水素結合が破壊さルて脱水和を起こ
し、該ポリビニルメチルエーテル分子は疎水性となって
水に不溶化するという性質を■している。The polyvinyl methyl ether used in the present invention is usually vinyl methyl ether, for example, BF3. Engineering 2
, AtClt, , FeC45, etc. are used as an initiator for cationic polymerization. This thing is
In the presence of water, at temperatures lower than the phase transition temperature, water hydrates due to hydrogen bonds and becomes water-soluble; at temperatures above the phase transition temperature, the hydrogen bonds are broken and dehydration occurs, causing the Polyvinyl methyl ether molecules have the property of becoming hydrophobic and insoluble in water.
本発明においては、ポリビニルメチルエーテル水溶液の
濃度は５〜５０重量係の範囲にあることが必要である。In the present invention, the concentration of the aqueous polyvinyl methyl ether solution must be in the range of 5 to 50% by weight.
この濃度が５重量％未満では薄すぎて実用的でなく、ま
た５０重量％を超えると粘度が上昇して取り扱いにりく
、かつ架橋をスムースに行うことができなくなる。If this concentration is less than 5% by weight, it is too thin to be practical, and if it exceeds 50% by weight, the viscosity increases, making it difficult to handle and crosslinking cannot be carried out smoothly.
ポリビニルメチルエーテルの相転移温度は通常３２〜４
０℃の範囲であるが、この水溶液に、例えば塩化ナトリ
ウムや塩化カルシウムなどの無機塩類、酢酸ナトリウム
やクエン酸ナトリウムなどの有機塩類、アルギン酸ナト
リウムやポリアクリル酸ナトリウムなどの高分子電解質
などを添加することにより、該相転移温′ｅＬヲ低下さ
せることができるし、またメタノール、エタノール、エ
チレングリコール、グリセリンなどの水溶性アルコール
類や、アセトンのような水溶性ケトン類などを添加する
ことによって、該相転移温度を上昇させることもできる
。すなわち、これらの添加剤の種類や量全適宜選ぶこと
により、該ポリビニルメチルエーテルの相転移温度金あ
る程度の範囲で任意に変えることができる。The phase transition temperature of polyvinyl methyl ether is usually 32 to 4
In the range of 0°C, for example, inorganic salts such as sodium chloride and calcium chloride, organic salts such as sodium acetate and sodium citrate, and polymer electrolytes such as sodium alginate and sodium polyacrylate are added to this aqueous solution. By adding water-soluble alcohols such as methanol, ethanol, ethylene glycol, and glycerin, and water-soluble ketones such as acetone, the phase transition temperature 'eL can be lowered. It is also possible to increase the phase transition temperature. That is, by appropriately selecting the types and amounts of these additives, the phase transition temperature of the polyvinyl methyl ether can be changed within a certain range.
本発明においては、前記ポリビニルメチルエーテル水溶
液を所要形状の容器に入几、その温度をポリビニルメチ
ルエーテルの相転移温度付近に維持シ、該ポリビニルメ
チルエーテルが分離、沈殿しない程度にミクロ相分離を
起こさせた状態で、ガンマ線又は電子線を照射すること
によシ、該ポリビニルメチルエーテルの架橋ゲルを生成
させる。In the present invention, the polyvinyl methyl ether aqueous solution is placed in a container of a desired shape, and its temperature is maintained near the phase transition temperature of the polyvinyl methyl ether to cause microphase separation to an extent that the polyvinyl methyl ether does not separate or precipitate. In this state, a crosslinked gel of the polyvinyl methyl ether is produced by irradiating it with gamma rays or electron beams.
このようにして得らｎたポリビニルメチルエーテル架橋
ゲルは、ミクロ相分離による微細な空孔’ｔＷしており
、水の存在下において温度により可逆的に形態が変化す
る。すなわち、該架橋ゲルは。The polyvinyl methyl ether crosslinked gel thus obtained has fine pores due to microphase separation, and its shape reversibly changes depending on temperature in the presence of water. That is, the crosslinked gel.
相転移温度より低い温度では水を吸収して膨潤し、また
相転移温度以上の温度では水を放出して収縮する。この
ような温度に対する応答性については。At temperatures below the phase transition temperature, it absorbs water and swells; at temperatures above the phase transition temperature, it releases water and contracts. Regarding this kind of responsiveness to temperature.
該架橋ゲルは、相転移温度より低い温度で架橋して得ら
几たゲルに比較して、相転移に伴う水の吸収、放出が微
細な空孔を通じて速やかに行わｎるために、極めて優１
ている。The cross-linked gel is extremely superior in comparison to a solid gel obtained by cross-linking at a temperature lower than the phase transition temperature, because water absorption and release accompanying the phase transition occur quickly through fine pores. 1
ing.
本発明においては、生成したゲルの強度や熱伝導性を向
上させるために、該ポリビニルメチルエーテル水溶液に
、所望により例えば金属粉、酸化鉄、カーボンブランク
に繊維などのフィラーを添加して、ガンマ線又は電子線
を照射することができる。In the present invention, in order to improve the strength and thermal conductivity of the resulting gel, fillers such as metal powder, iron oxide, carbon blank, and fibers are optionally added to the polyvinyl methyl ether aqueous solution, and gamma rays or It can be irradiated with an electron beam.
発明の効果
本発明の温度応答性多孔質ゲルは、微細な空孔ヲ有する
ポリビニルメチルエーテルの架橋ゲルから成り、かつ水
の存在下において温度により可逆的に形態全変化しつる
、温度応答性に優ｎたものであって、メカノケミカル材
料として１例えばエネルギー変換、エネルギー貯蔵、ア
クチェーター、センサー、吸脱木材、放水材、玩具など
への利用が可能である。Effects of the Invention The temperature-responsive porous gel of the present invention is composed of a crosslinked gel of polyvinyl methyl ether having fine pores, and has a temperature-responsive property that completely changes its shape reversibly depending on temperature in the presence of water. It is an excellent material and can be used as a mechanochemical material, such as energy conversion, energy storage, actuators, sensors, absorbent and desorbable wood, water discharge materials, toys, etc.
実施例 次に実施例によって本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１
ポリビニルメチルエーテルの２０重量％水溶液を横１ｚ
、縦１６ｎ１高さ５６ｎのポリスチレン製の容器に人ｆ
′Ｌ、 ３２．５℃から４２．５℃まで２．５℃／時
の速度で昇温しながら、１０メガランドのガンマ線を照
射することにより多孔性の架橋ゲルを製造した。このゲ
ルはポリビニルメチルエーテル水溶液と同様に、３７℃
で相転移を起こし、２０℃と４０℃とでは、約１０倍の
体積変化を示し、温度により可逆的に低温では膨潤、高
温では収縮した。Example 1 A 20% by weight aqueous solution of polyvinyl methyl ether was poured horizontally 1z
, a person f is placed in a polystyrene container with a length of 16n and a height of 56n.
'L, a porous crosslinked gel was produced by irradiating with 10 Megaland gamma rays while increasing the temperature from 32.5°C to 42.5°C at a rate of 2.5°C/hour. This gel was heated at 37°C like the polyvinyl methyl ether aqueous solution.
It underwent a phase transition at 20°C and 40°C, exhibiting a volume change of about 10 times, and reversibly swelled at low temperatures and contracted at high temperatures.
その応答時間は１．２分と短く、温度応答性は良好であ
った。The response time was as short as 1.2 minutes, and the temperature response was good.
一万、２５℃の一定温度でのガンマ線照射にて製造した
架橋ゲルは上記のゲルと同様に温度の上下によυ膨潤、
収縮するが、ゲルの構造は均一で、その応答時間は２．
５時間と長く、温度応答性が劣るものであった。The cross-linked gel produced by gamma ray irradiation at a constant temperature of 25℃ swells as the temperature rises and falls, similar to the above gel.
Although it shrinks, the gel structure is uniform and its response time is 2.
The test time was as long as 5 hours, and the temperature response was poor.
実施例２
ポリビニルメチルエーテルの３０重量％水浴液１０重量
部と、四三酸化鉄粉末５軍事部を十分に混合したのち、
直径３ｃｒｎ、高さ６ｃｍのガラス容器（（入ｎ、実施
例１と同様の温度、及び照射条件でガンマ線を照射し、
多孔性の架橋ゲルを製造した。Example 2 After thoroughly mixing 10 parts by weight of a 30% by weight water bath solution of polyvinyl methyl ether and 5 parts by weight of triiron tetroxide powder,
A glass container with a diameter of 3 crn and a height of 6 cm was irradiated with gamma rays at the same temperature and irradiation conditions as in Example 1.
A porous crosslinked gel was produced.
このゲルは、実施例１の場合と同様に２０℃と４０℃と
では約１０倍の体積変化を示し、温度の上下により可逆
的に膨潤、収縮を繰り返す。その温度応答時間は約５分
であり、四三酸化鉄を含まない多孔性ゲルに比較して１
．５倍速かった。特に、膨潤ゲルを高周波加熱した場合
、その収縮時間は８秒と非常に短く、充填物の効果が見
られた。As in Example 1, this gel exhibits a volume change of about 10 times between 20° C. and 40° C., and reversibly swells and contracts as the temperature rises and falls. Its temperature response time is about 5 minutes, compared to porous gel without triiron tetroxide.
．． It was five times faster. In particular, when the swollen gel was subjected to high-frequency heating, the shrinkage time was as short as 8 seconds, indicating the effect of the filling.
実施例３
ポリビニルメチルエーテルの３０重量％水溶液１０重量
部と、５重量％の食塩水５重量部とを混合した溶液を、
実施例１に記載と同様の容器にいれ、２５℃に加熱しな
がら直線加速器を用い、電子エネルギー６．２ＭｅＶ、
電子流密度３４μＡ／１１ｗａｇにて４０秒間電子線を
照射することにより。Example 3 A solution of 10 parts by weight of a 30% by weight aqueous solution of polyvinyl methyl ether and 5 parts by weight of 5% by weight saline was mixed with
It was placed in a container similar to that described in Example 1, and heated to 25°C using a linear accelerator, with an electron energy of 6.2 MeV.
By irradiating an electron beam for 40 seconds at an electron current density of 34 μA/11 wag.
実施例１と同様の多孔性の架橋ゲルを得ることができ、
温度に対する挙動も実施例１の場合と同様であった。A porous crosslinked gel similar to that in Example 1 can be obtained,
The behavior with respect to temperature was also similar to that of Example 1.
実施例４
ポリビニルメチルエーテルめ３ｏ重量％水溶液ＪＯｔ量
部と７０重量％メタノール水溶液５０重量部とを混会し
、実施例１に記載と同様の容器に鴫
い−ｎ、４０℃から５０℃まで２．５℃／；の昇温速度
で昇温しながら、実施例１と同様の照射条件でガンマ線
照射を行い、実施例１と同様の多孔性架橋ゲルを製造し
た。このゲルの温度に対する挙動も、実施例１の場合と
同様てあった。Example 4 Parts of a 30% by weight aqueous solution of polyvinyl methyl ether JOt and 50 parts by weight of a 70% by weight aqueous methanol solution were mixed, and the mixture was poured into a container similar to that described in Example 1 at a temperature of 40°C to 50°C. Gamma ray irradiation was performed under the same irradiation conditions as in Example 1 while increasing the temperature at a rate of 2.5°C/; to produce a porous crosslinked gel similar to that in Example 1. The temperature behavior of this gel was also similar to that of Example 1.
特許出願人 工業技術院長 等々カ 達指定代理
人 工業技術院繊維高分子材ｉ研究所長岡 太
：、・ 昭
１．１、“１、Patent applicant Futoshi Nagaoka, Director of the Agency of Industrial Science and Technology, etc. Designated agent: Futoshi Nagaoka, Institute of Textile and Polymer Materials, Agency of Industrial Science and Technology
:,・ Showa 1.1, “1,
Claims (1)
橋ゲルから成り、かつ水の存在下において温度により可
逆的に形態変化しうる温度応答性多孔質ゲル。 ２ ポリビニルメチルエーテル５〜５０重量％を含有す
る水溶液を所要形状に保ち、その温度を該ポリビニルメ
チルエーテルの相転移温度付近に維持して、ガンマ線又
は電子線を照射することを特徴とする、微細な空孔を有
するポリビニルエーテルの架橋ゲルから成り、かつ水の
存在下において温度により可逆的に形態変化しうる温度
応答性多孔質ゲルの製造方法。[Scope of Claims] 1. A temperature-responsive porous gel consisting of a cross-linked gel of polyvinyl methyl ether having fine pores and capable of reversibly changing its shape depending on temperature in the presence of water. 2. A microscopic method characterized by maintaining an aqueous solution containing 5 to 50% by weight of polyvinyl methyl ether in a desired shape, maintaining its temperature near the phase transition temperature of the polyvinyl methyl ether, and irradiating it with gamma rays or electron beams. A method for producing a temperature-responsive porous gel, which is made of a crosslinked gel of polyvinyl ether having pores, and whose shape can be reversibly changed by temperature in the presence of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9383286A JPS62250940A (en) | 1986-04-23 | 1986-04-23 | Temperature responsive porous gel and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9383286A JPS62250940A (en) | 1986-04-23 | 1986-04-23 | Temperature responsive porous gel and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62250940A true JPS62250940A (en) | 1987-10-31 |
| JPH0251936B2 JPH0251936B2 (en) | 1990-11-09 |
Family
ID=14093363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9383286A Granted JPS62250940A (en) | 1986-04-23 | 1986-04-23 | Temperature responsive porous gel and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62250940A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031498A1 (en) * | 1994-05-13 | 1995-11-23 | University Of Cincinnati | Microporous fast response gels and methods of use |
| US6030442A (en) * | 1994-05-13 | 2000-02-29 | University Of Cincinnati | Microporous fast response gels and methods of use |
| CN107981967A (en) * | 2016-10-26 | 2018-05-04 | 袁暾 | A kind of cold compress application for carrying silicate particulate |
-
1986
- 1986-04-23 JP JP9383286A patent/JPS62250940A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031498A1 (en) * | 1994-05-13 | 1995-11-23 | University Of Cincinnati | Microporous fast response gels and methods of use |
| US6030442A (en) * | 1994-05-13 | 2000-02-29 | University Of Cincinnati | Microporous fast response gels and methods of use |
| CN107981967A (en) * | 2016-10-26 | 2018-05-04 | 袁暾 | A kind of cold compress application for carrying silicate particulate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0251936B2 (en) | 1990-11-09 |
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