JPH01270936A - Manufacture of temperature responsive porous gel - Google Patents
Manufacture of temperature responsive porous gelInfo
- Publication number
- JPH01270936A JPH01270936A JP9808388A JP9808388A JPH01270936A JP H01270936 A JPH01270936 A JP H01270936A JP 9808388 A JP9808388 A JP 9808388A JP 9808388 A JP9808388 A JP 9808388A JP H01270936 A JPH01270936 A JP H01270936A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- gel
- methyl ether
- polyvinyl methyl
- phase transition
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims abstract description 39
- 230000007704 transition Effects 0.000 claims abstract description 29
- 238000010894 electron beam technology Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 230000001678 irradiating effect Effects 0.000 claims description 8
- 230000004044 response Effects 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 238000004132 cross linking Methods 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 8
- 238000005191 phase separation Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 48
- 239000000463 material Substances 0.000 description 15
- 230000008602 contraction Effects 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 230000002522 swelling effect Effects 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 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
- 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
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material 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
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Colloid Chemistry (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
態変化しうる温度応答性多孔質ゲルの製造方法に関する
ものである。更に詳しくは、本発明は、メカノケミカル
材料として、例えばエネルギー変換、エネルギー貯蔵、
アクチエーター、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メチルエ
ーテルの架橋ゲルから成る温度応答性に優れた多孔質ゲ
ルの改良された製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing a temperature-responsive porous gel that can reversibly change its shape depending on temperature in the presence of water. More specifically, the present invention provides mechanochemical materials, such as energy conversion, energy storage,
Temperature-responsive material made of cross-linked polyvinyl methyl ether gel that can be used for actuators, sensors, absorbent wood, water discharge materials, toys, etc., which can reversibly swell at low temperatures and contract at high temperatures in the presence of water. The present invention relates to an improved method for producing a porous gel with excellent properties.
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、無機材
料では形状記憶合金が知られており、このものは、種々
の分野で利用されはじめている。−方、存機材料におい
ては、ポリメタクリル酸ゲルがポリエチレングリコール
水溶液中で温度を変化させることにより、可逆的に伸縮
することが知られている〔「ジャーナル・オプ・ポリマ
ー・サイエンス（Ｊ Ｐｏｌｙｍｅｒ ５ｃｉ） 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
することが報告されており〔「フィジカル・レビュー、
レターズ（Ｐｈｙｓｉｃａｌ Ｒｅｖｉｅｗ Ｌｅｔｔ
ｅｒｓ）Ｊ第４０巻、第８２０ページ（１９７８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、化学バルブ、エネ
ルギー変換、エネルギー貯蔵、センサーなどへの応用が
挙げられている。BACKGROUND OF THE INVENTION Conventionally, shape memory alloys have been known as inorganic materials whose shape changes with temperature, and these are beginning to be used in various fields. - On the other hand, among existing materials, it is known that polymethacrylic acid gel reversibly expands and contracts by changing the temperature in an aqueous polyethylene glycol solution [Journal of Polymer Science (J Polymer 5ci). ) J
Vol. 15, p. 255 (1977)], and it has also been reported that polyacrylamide gel swells in a water-acetone system by increasing the temperature and shrinks by decreasing the temperature [Physical Review,
Letters (Physical Review Letts)
ers) J Volume 40, Page 820 (1978)]
The report also cites potential uses of this phenomenon for applications such as chemical engines, artificial muscles, chemical valves, energy conversion, energy storage, and sensors.
発明が解決しようとする課題
これらの温度応答性有機材料は、いずれも高分子ゲルか
らなり、該材料が温度により膨潤、収縮する場合には、
ゲルを構成し７ている液体の吸収、放出を伴い、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り、
その応答速度はゲルの大きさの２乗に比例することが知
られている〔［フィジカル・レビュー ・レターズ（Ｐ
ｈｙｓｉｃａｌＲｅｖｉｅｗ Ｌｅｔｔｅｒｓ） Ｊ第
５５巻、第２４５５ページ（１９８５年）〕、つまり、
ゲルの大きさが小さければ小さいほど、該材料の応答速
度は速くなる。Problems to be Solved by the Invention These temperature-responsive organic materials are all made of polymer gels, and when the materials swell or contract due to temperature,
Accompanied by the absorption and release of the liquid that constitutes the gel, the diffusion of this liquid within the gel determines the temperature response of the material,
It is known that the response speed is proportional to the square of the gel size [[Physical Review Letters (P
HysicalReview Letters) J Volume 55, Page 2455 (1985)], that is,
The smaller the size of the gel, the faster the response speed of the material.
しかし、一方、該材料の強度の面からみると、ゲルの大
きさが大きければ大きいほど強くなる。すなわち、該材
料の応答速度を上げようとすると、該材料の強度が弱く
なり、また、該材料の強度を高めようとすると、該材料
の応答速度が遅くなるという問題点を有している。However, in terms of the strength of the material, the larger the gel size, the stronger it becomes. That is, if an attempt is made to increase the response speed of the material, the strength of the material becomes weak, and if an attempt is made to increase the strength of the material, the response speed of the material becomes slow.
ｉＩ題を解決するための手段
本発明者らは前記の問題点を解決するために、鋭意研究
を重ねた結果、小さなゲルが多数集合し、そして、その
ゲルとゲルとが空孔により隔てられている構造、すなわ
ち、微細な空孔を持つ多孔質ゲルを調製することにより
、目的を達成することができるのではと考えた。iI Means for Solving the Problem In order to solve the above problem, the inventors of the present invention have conducted intensive research and found that a large number of small gels aggregate and the gels are separated by holes. We thought that we might be able to achieve this goal by preparing a porous gel with a similar structure, that is, microscopic pores.
そこで、本発明者らはガンマ線または電子線を照射する
ことによりゲル化し、相転移温度（３８℃付近）を持つ
ポリビニルメチルエーテル水溶液に着目し鋭意研究を重
ねた結果、その温度を該ポリビニルメチルエーテル水溶
液の相転移温度付近に維持して、ガンマ線または電子線
を照射することによる、微細な空孔を有するポリビニル
メチルエーテルの架橋ゲルの製造方法を見出した（特願
昭６ｌ−９３８３２）。Therefore, the present inventors focused on polyvinyl methyl ether aqueous solutions that gel by irradiation with gamma rays or electron beams and have a phase transition temperature (near 38°C), and as a result of extensive research, they found that the temperature of the polyvinyl methyl ether We have discovered a method for producing a crosslinked polyvinyl methyl ether gel having fine pores by maintaining the temperature near the phase transition temperature of an aqueous solution and irradiating it with gamma rays or electron beams (Japanese Patent Application No. 61-93832).
ところが、この製造方法で多孔質ゲルを製造する場合、
ガンマ線または電子線の照射線量と相転移温度付近での
反応温度を厳しく管理する必要があり、条件により、均
質なゲルあるいは、容器内に凝集したゲルが生成する場
合があり、製造上不安定な面があることがわかった。However, when producing porous gel using this production method,
It is necessary to strictly control the irradiation dose of gamma rays or electron beams and the reaction temperature near the phase transition temperature, and depending on the conditions, a homogeneous gel or a gel that aggregates in the container may be formed, which may result in unstable manufacturing. I found out that there is a side to it.
そこで、さらに鋭意検討を重ねた結果、ポリビニルメチ
ルエーテル水溶液の相転移温度に到達するまでの、ガン
マ線または電子線の照射＆ｌＩＩが多いと、相分離が起
こる前に架線の度合いが多くなるため均質なゲルが得ら
れ、そのゲルの水の存在下での温度応答性は数時間から
数日間と低いこと、また、ポリビニルメチルエーテル水
溶液の相転移温度に到達するまでの、ガンマ線または電
子線の照射線量が少ないと、架橋の度合いが少ないため
、相転移温度以上では急激に相分離がおこり、容器内に
凝集するため、所望の形状を得ることができないことが
判明した。Therefore, as a result of further intensive studies, we found that if there is a large amount of gamma ray or electron beam irradiation until the phase transition temperature of the polyvinyl methyl ether aqueous solution is reached, the degree of overhead wire will increase before phase separation occurs, resulting in a homogeneous product. A gel is obtained, and the temperature responsiveness of the gel in the presence of water is low, ranging from several hours to several days, and the irradiation dose of gamma rays or electron beams until the phase transition temperature of the polyvinyl methyl ether aqueous solution is reached. It has been found that if there is a small amount, the degree of crosslinking will be small, and as a result, phase separation will occur rapidly above the phase transition temperature and agglomeration will occur in the container, making it impossible to obtain the desired shape.
ところが、ポリビニルメチルエーテル水溶液をその相転
移温度より低い温度でガンマ線または電子線を照射して
あらかじめ適度に架橋を入れた後、続いてその相転移温
度より高い温度でガンマ線または電子線を照射すると、
架橋の速度と相分離の速度がうまくバランスして微細な
空孔を有する多孔質のゲルが得られ、その温度応答性は
高く数秒間から数分間であることを見いだした。However, if a polyvinyl methyl ether aqueous solution is irradiated with gamma rays or electron beams at a temperature lower than its phase transition temperature to form a moderate amount of crosslinking in advance, and then irradiated with gamma rays or electron beams at a temperature higher than its phase transition temperature,
We found that a porous gel with fine pores was obtained by well balancing the speed of crosslinking and phase separation, and that its temperature response was high, ranging from several seconds to several minutes.
つまり、相転移温度に達するまでの、ガンマ線または電
子線の照射′ｖＡ！！ｋを確実に制御することが微細な
空孔を持つ多孔質ゲルを安定に製造するための必須条件
であり、この知見に基づき本発明を完成するに至った。In other words, irradiation with gamma rays or electron beams until the phase transition temperature is reached 'vA! ! Reliably controlling k is an essential condition for stably producing a porous gel having fine pores, and based on this knowledge, the present invention was completed.
すなわち、本発明は、ポリビニルメチルエーテルを含有
する水溶液を所要形状に保ち、まずその’１７４度を該
ポリビニルメチルエーテル水溶液の相転移ｌＨ度より低
い温度を保ち、ガンマ線または電子線を照射した後、そ
の温度を該ポリビニルメチルエーテル水）合液の相転移
温度より高い温度に保ち、更にガンマ線または電子線を
照射することを特徴とするポリビニルメチエーテルの架
橋ゲルからなる温度応答性多孔質ゲルの製造方法に関す
るものである。That is, the present invention maintains an aqueous solution containing polyvinyl methyl ether in a desired shape, first keeps its temperature at 174 degrees lower than the phase transition lH degree of the polyvinyl methyl ether aqueous solution, and then irradiates it with gamma rays or electron beams. Production of a temperature-responsive porous gel made of a crosslinked gel of polyvinyl methyl ether, which is maintained at a temperature higher than the phase transition temperature of the polyvinyl methyl ether/water mixture and further irradiated with gamma rays or electron beams. It is about the method.
本発明において用いるポリビニルメチルエーテルは、通
常メチルビニルエーテルを、例えば、ＢＦ ３ 、Ｉ
ｚ 、Ａ Ｉ Ｃ１ｚ 、Ｆ ＠ Ｃ１ｓなどを開始剤
としてカチオン重合させることにより得られる。The polyvinyl methyl ether used in the present invention is usually methyl vinyl ether, for example, BF 3 , I
It can be obtained by cationic polymerization using z, A I C1z, F@C1s, etc. as an initiator.
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、ま
た相転移温度より高い温度では水素結合が破壊されて脱
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となる性質を有している。In the presence of water, at temperatures lower than the phase transition temperature, water becomes hydrated due to hydrogen bonds and becomes water-soluble; at temperatures higher than the phase transition temperature, hydrogen bonds are broken and dehydration occurs, resulting in Polyvinyl methyl ether molecules have the property of being 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％の範囲にあることが望ましい、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％を越えると粘度が上昇して取り扱いに＜＜、
かつ架線をスムーズに行うことができな（なる。In the present invention, the concentration of the polyvinyl methyl ether aqueous solution is preferably in the range of 5 to 50% by weight; 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 will be low. Rise and handle <<,
Also, the overhead lines cannot be installed smoothly.
また、本発明においてポリビニルメチルエーテルを含有
する水溶液を所要形状に保ち、その温度を該ポリビニル
メチルエーテル水溶液の相転移温度より低い温度を保ち
、ガンマ線または電子線を照射する際、その照射線量に
該ポリビニルメチルエーテル水溶液の濃度により異なる
が０．５−２．５メガランド、好ましくは１−２メガラ
ンドである。In addition, in the present invention, the aqueous solution containing polyvinyl methyl ether is kept in a desired shape and its temperature is kept lower than the phase transition temperature of the polyvinyl methyl ether aqueous solution, and when irradiating with gamma rays or electron beams, the irradiation dose is Although it varies depending on the concentration of the polyvinyl methyl ether aqueous solution, it is 0.5-2.5 megalands, preferably 1-2 megalands.
すなわち、照射線量がこれより少ない場合には、続いて
その温度を該ポリビニルメチルエーテル水溶液の相転移
温度より高い温度を保ち、更にガンマ線または電子線を
照射した場合、架橋の度合いが少ないため急激に相分離
が起こり所望の形状を得ることができない、また、照射
線量が前記の量より多い場合には、続いてその温度を該
ポリビニルメチルエーテル水溶液の相転移温度より高い
温度に保ち、更にガンマ線または電子線を照射した場合
、架橋の度合いが多いため相分離が起こりにくく均質な
ゲルしか得られない。In other words, when the irradiation dose is less than this, the temperature is maintained higher than the phase transition temperature of the polyvinyl methyl ether aqueous solution, and when gamma rays or electron beams are further irradiated, the degree of crosslinking is small, so If phase separation occurs and the desired shape cannot be obtained and the irradiation dose is higher than the above-mentioned amount, the temperature is subsequently maintained at a temperature higher than the phase transition temperature of the polyvinyl methyl ether aqueous solution, and gamma rays or When irradiated with an electron beam, the degree of crosslinking is high, so phase separation is difficult to occur and only a homogeneous gel can be obtained.
また、本発明においてポリビニルメチルエーテル水溶液
にガンマ線または電子線を照射するその総照射線量は５
メガランド以上が好ましい。５メガランド未満では、使
用に際し実用的でなくかつ均質なゲルしか得られない。In addition, in the present invention, the total irradiation dose when gamma rays or electron beams are irradiated to the polyvinyl methyl ether aqueous solution is 5
Megaland or higher is preferred. If it is less than 5 megalands, it is not practical to use and only a homogeneous gel is obtained.
さらに、本発明においてポリビニルメチルエーテル水溶
液の相転移温度より低い温度とは、０℃以上、３８℃未
満を意味し好ましくは１０℃ないし３０℃の温度を意味
し、また、ポリビニルメチルエーテル水溶液の相転移温
度より高い温度とは３８℃以上を意味し好ましくは３８
℃ないし５０℃の温度を意味する。Furthermore, in the present invention, the temperature lower than the phase transition temperature of the polyvinyl methyl ether aqueous solution means a temperature of 0°C or more and less than 38°C, preferably 10°C to 30°C, and also a temperature lower than the phase transition temperature of the polyvinyl methyl ether aqueous solution. Temperature higher than the transition temperature means 38°C or higher, preferably 38°C.
It means a temperature between 50°C and 50°C.
本発明の方法により得られたポリビニルメチルエーテル
架橋ゲルは、微細を空孔を存しており、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、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、該
架橋ゲルは、相転移温度より低い温度で架橋して得られ
た均質なゲルに比較して、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れるために、極めて
優れている。そして膨潤、収縮の繰り返しによるゲルの
劣化は殆んど認められなかった。The polyvinyl methyl ether crosslinked gel obtained by the method of the present invention has fine pores, and its shape reversibly changes depending on temperature in the presence of water. That is, the crosslinked gel absorbs water and swells at a temperature lower than the phase transition temperature, and releases water and contracts at a temperature higher than the phase transition temperature. Regarding the responsiveness to such temperature, the cross-linked gel has fine pores that absorb and release water during phase transition, compared to a homogeneous gel obtained by cross-linking at a temperature lower than the phase transition temperature. It is extremely good because it can be done quickly through the process. Almost no deterioration of the gel due to repeated swelling and contraction was observed.
本発明方法により得られた温度応答性多孔質ゲルは、微
細を空孔を有するポリビニルメチルニーチルの架橋ゲル
からなり、かつ水の存在下において温度により可逆的に
変化しうる、温度応答性に優れたものであって、メカノ
ケミカル材料として、例えばエネルギー変換、エネルギ
ー貯蔵、アクチエーター、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。The temperature-responsive porous gel obtained by the method of the present invention is composed of a crosslinked gel of polyvinylmethylnityl having fine pores, and has a temperature-responsive property that can be reversibly changed 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 desorbing wood, water release 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３０重量％水溶液を縦ｌｅ
ａ、横１ｅ１１．高さ５ａａのポリスチレン製の容器に
入れ、２５℃で１．２５メガランドのガンマ線照射した
後、続いて３８．５℃で８．８２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、３
８℃付近で相転移を起こす。Example 1 A 30% by weight aqueous solution of polyvinyl methyl ether was poured vertically.
a, horizontal 1e11. A porous crosslinked gel was produced by placing it in a polystyrene container with a height of 5 aa and irradiating it with gamma rays of 1.25 Megaland at 25°C, followed by irradiation with gamma rays of 8.82 Megaland at 38.5°C. . This gel, like the polyvinyl methyl ether aqueous solution,
A phase transition occurs around 8°C.
そして、温度により可逆的に変化し、低温では膨潤、高
温では収縮し、１０℃と４０’Ｃでは、約１５倍の体積
変化を示した。そして、その応答時間は約３０秒と短く
、温度応答性は良好であった。It changed reversibly depending on temperature, swelling at low temperatures and contracting at high temperatures, and showed a volume change of about 15 times at 10°C and 40'C. The response time was as short as about 30 seconds, and the temperature response was good.
また、膨潤、収縮の繰り返しによるゲル劣化は殆んど認
められなかった。In addition, almost no gel deterioration due to repeated swelling and contraction was observed.
実施例２
ポリビニルメチルエーテルの３０重量％水溶液を約ｊｃ
ｓ、横１０、高さ５Ｃ１ｌのポリスチレン製の容器にい
れ、２５℃で１．０５メガランドのガンマ線照射した後
、続いて３８６５℃で１Ｏ９５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することが
でき、その温度に対する挙動は実施例１の場合と同様で
あり、その応答時間は４５秒と短＜、温度応答性は良好
であった。また、膨潤、収縮の繰り返しによるゲルの劣
化は殆んど認められなかった。Example 2 A 30% by weight aqueous solution of polyvinyl methyl ether was
A porous cross-linked gel was produced by placing it in a polystyrene container with a width of 10 s and a height of 5 C1l, and irradiating it with gamma rays of 1.05 megaland at 25°C, and then irradiating it with gamma rays of 1095 megaland at 3865°C. The behavior with respect to temperature was similar to that of Example 1, the response time was as short as 45 seconds, and the temperature response was good. Further, almost no deterioration of the gel due to repeated swelling and contraction was observed.
実施例３
ポリビニルメチルエーテルの３０重量％水溶液を約しＬ
横ｌｅａ、高さ５１のポリスチレン製の容器にいれ、２
５℃で１．８８メガランドのガンマ線照射した後、続い
て４０℃で８．８２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することができ、その
温度に対する挙動は実施例１の場合と同様であり、その
応答速度は５０秒と短く、温度応答性は良好であった。Example 3 Approximately 30% by weight aqueous solution of polyvinyl methyl ether
Place in a polystyrene container with width lea and height 51,
A porous cross-linked gel can be produced by irradiating with gamma rays of 1.88 Megaland at 5°C, followed by gamma rays of 8.82 Megaland at 40°C, and its temperature behavior is similar to that of Example 1. The response speed was as short as 50 seconds, and the temperature response was good.
また、膨潤、収縮の繰り返しによるゲルの劣化は殆んど
認められなかった。Further, almost no deterioration of the gel due to repeated swelling and contraction was observed.
実施例４
実施例１においてポリビニルメチルエーテルの３０重量
％水溶液を用いる代わりにポリビニルメチルエーテルの
１０重Ｍ％水溶液を用いて、実施例１と同様の操作を行
うことにより多孔性の架橋ゲルを製造することができ、
その温度に対する挙動は実施例１の場合と同様であり、
１０℃と４０℃では、約１０倍の体積変化を示した。そ
の応答時間は６０秒と短（、温度応答性は良好であった
。Example 4 A porous crosslinked gel was produced by performing the same operation as in Example 1, using a 10% by weight aqueous solution of polyvinyl methyl ether instead of using the 30% by weight aqueous solution of polyvinyl methyl ether in Example 1. can,
Its behavior with respect to temperature is similar to that of Example 1,
At 10°C and 40°C, the volume changed about 10 times. The response time was as short as 60 seconds (and the temperature response was good).
また、膨潤、収縮の繰り返しによるゲルの劣化は殆んど
認められなかった。Further, almost no deterioration of the gel due to repeated swelling and contraction was observed.
実施例５
実施例１においてポリビニルメチルエーテルの３０重量
％水溶液を用いる代わりにポリビニルメチルエーテルの
５０重量％水溶液を用いて、実施例１と同様の操作を行
うことにより多孔性の架橋ゲルを製造することができ、
その温度に対する挙動は実施例１の場合と同様であり、
１０℃と４０℃では、約１６倍の体積変化を示した。そ
の応答時間は３０秒と短く、温度応答性は良好であった
。Example 5 A porous crosslinked gel is produced by carrying out the same operation as in Example 1, using a 50% by weight aqueous solution of polyvinyl methyl ether instead of using the 30% by weight aqueous solution of polyvinyl methyl ether in Example 1. It is possible,
Its behavior with respect to temperature is similar to that of Example 1,
At 10°C and 40°C, the volume changed about 16 times. The response time was as short as 30 seconds, and the temperature response was good.
また、膨潤、収縮の繰り返しによるゲルの劣化は殆んど
認められなかった。Further, almost no deterioration of the gel due to repeated swelling and contraction was observed.
実施例６
ポリビニルメチルエーテルの３０重量％水溶液を実施例
１と同様の容器に入れ、２０℃で１．５メガラツドの電
子線を照射した後、続いて４５℃で８．５メガランドの
電子線を照射することにより多孔性の架橋ゲルを製造す
ることができ、その温度に対する挙動は実施例１の場合
と同様でありその応答時間は４５秒と短く、温度応答性
は良好であった。また、膨潤、収縮の繰り返しによるゲ
ルの劣化は殆んど認められなかった。Example 6 A 30% by weight aqueous solution of polyvinyl methyl ether was placed in the same container as in Example 1 and irradiated with an electron beam of 1.5 megarads at 20°C, followed by an electron beam of 8.5 megarads at 45°C. A porous crosslinked gel could be produced by irradiation, and its behavior with respect to temperature was similar to that of Example 1, with a short response time of 45 seconds and good temperature responsiveness. Further, almost no deterioration of the gel due to repeated swelling and contraction was observed.
発明の効果
物理的強度が十分高く温度に対する応答速度にすぐれた
ポリビニルメチルエーテルの多孔質ゲルの製造方法が確
立された。Effects of the Invention A method for producing a porous gel of polyvinyl methyl ether which has sufficiently high physical strength and excellent response speed to temperature has been established.
特許出願人 工業技術院長 飯塚幸三
指定代理人 工業技術院繊維高分子材料研究所長 須田
昌男Patent applicant: Director of the Agency of Industrial Science and Technology Kozo Iizuka Designated representative: Director of the Textile and Polymer Materials Research Institute, Agency of Industrial Science and Technology Masao Suda
Claims (1)
形状に保ち、まずその温度を該ポリビニルメチルエーテ
ル水溶液の相転移温度より低い温度に保ち、ガンマ線ま
たは電子線を照射した後、その温度を該ポリビニルメチ
ルエーテル水溶液の相転移温度より高い温度に保ち、更
にガンマ線または電子線を照射することを特徴とするポ
リビニルメチルエーテルの架線ゲルからなる温度応答性
多孔質ゲルの製造方法。1. Keep an aqueous solution containing polyvinyl methyl ether in the desired shape, first maintain its temperature at a temperature lower than the phase transition temperature of the polyvinyl methyl ether aqueous solution, and after irradiating with gamma rays or electron beams, reduce the temperature to the polyvinyl methyl ether A method for producing a temperature-responsive porous gel made of a polyvinyl methyl ether catenary gel, which comprises maintaining the temperature at a temperature higher than the phase transition temperature of an aqueous solution and further irradiating it with gamma rays or electron beams.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63098083A JP2519971B2 (en) | 1988-04-22 | 1988-04-22 | Method for producing temperature-responsive porous gel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63098083A JP2519971B2 (en) | 1988-04-22 | 1988-04-22 | Method for producing temperature-responsive porous gel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01270936A true JPH01270936A (en) | 1989-10-30 |
| JP2519971B2 JP2519971B2 (en) | 1996-07-31 |
Family
ID=14210450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63098083A Expired - Lifetime JP2519971B2 (en) | 1988-04-22 | 1988-04-22 | Method for producing temperature-responsive porous gel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2519971B2 (en) |
Cited By (2)
| 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 |
-
1988
- 1988-04-22 JP JP63098083A patent/JP2519971B2/en not_active Expired - Lifetime
Cited By (2)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2519971B2 (en) | 1996-07-31 |
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