JPH0547256B2 - - Google Patents
Info
- Publication number
- JPH0547256B2 JPH0547256B2 JP16840287A JP16840287A JPH0547256B2 JP H0547256 B2 JPH0547256 B2 JP H0547256B2 JP 16840287 A JP16840287 A JP 16840287A JP 16840287 A JP16840287 A JP 16840287A JP H0547256 B2 JPH0547256 B2 JP H0547256B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl ether
- gel
- temperature
- polyvinyl methyl
- 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.)
- Expired - Lifetime
Links
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 16
- 230000007704 transition Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 229920006318 anionic polymer Polymers 0.000 claims description 9
- 238000005345 coagulation Methods 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 9
- 239000005518 polymer electrolyte Substances 0.000 claims description 9
- 229920001448 anionic polyelectrolyte Polymers 0.000 claims description 7
- 238000010894 electron beam technology Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000002166 wet spinning Methods 0.000 claims description 2
- 239000000499 gel Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 230000004043 responsiveness Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 239000000783 alginic acid Substances 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 229960001126 alginic acid Drugs 0.000 description 3
- 150000004781 alginic acids Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 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
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 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
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Colloid Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Measuring Temperature Or Quantity Of Heat (AREA)
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、温度変化に応
答して可逆的に形態変化、親水性／疎水性変化、
及び透明度変化しうる感温性ゲルの製造方法に関
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、例えばエネルギー変
換、エネルギー貯蔵、アクチエータ、センサー、
吸脱水材、放水材、玩具、親水性／疎水性変化材
料として、例えば分離膜、吸着剤、透明度変化材
料として、遮光材への利用が可能な、水の存在下
において低温で膨潤、親水性、透明、高温で収
縮、疎水性、不透明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を効果的に製造
する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides reversible morphological changes, hydrophilic/hydrophobic changes,
The present invention also relates to a method for producing a temperature-sensitive gel whose transparency can be changed. More specifically, the present invention is applicable to mechanochemical materials such as energy conversion, energy storage, actuators, sensors, etc.
Can be used as water absorption/desorption materials, water discharge materials, toys, hydrophilic/hydrophobic changing materials such as separation membranes, adsorbents, transparency changing materials, and light shielding materials.Swells at low temperatures in the presence of water and is hydrophilic. The present invention relates to a method for effectively producing a crosslinked polyvinyl methyl ether gel that is transparent, shrinks at high temperatures, becomes hydrophobic, and becomes opaque reversibly.
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。一方、有機材料では、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［「ジヤーナル・オブ・ポリマー・サイ
エンス（J.Polymer Sci.）」第15巻、第225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［「フイジカル・レビユー・レター
ズ（Physical Review Letters）」第40巻、第820
ページ（1978年）］、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。Conventional technology Conventionally, shape memory alloys have been known as inorganic materials that change their shape depending on temperature.
This product is beginning to be used in various fields. On the other hand, among organic materials, it is known that polymethacrylic acid gel reversibly expands and contracts by changing the temperature in an aqueous polyethylene glycol solution [J. Polymer Sci. ” Volume 15, Page 225 (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 [Physical Review Letters, Vol. 40, No. 820.
Page (1978)], the report lists potential applications for such phenomena in chemical engines, artificial muscles, chemical valves, energy conversion, energy storage, and sensors.
しかしながら、これらの感温性有機材料におい
ては、いずれもゲル状を呈しており、材料が温度
変化により膨潤、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を伴ない、この液体の
ゲル中の透過が該材料の感温性の律速となるため
応答性の良い材料を得るためには、ゲルの大きさ
を小さくしたり、細い繊維状のゲルを調製するこ
とが必要であるが、材料の成形法の面からまだ解
決されておらず、感温性の良い材料は得られてい
ない。 However, all of these temperature-sensitive organic materials have a gel-like appearance, and when the material swells or contracts due to temperature changes, this is accompanied by absorption or release of the liquid that makes up the gel. The permeation of a liquid through a gel determines the temperature sensitivity of the material, so in order to obtain a material with good responsiveness, it is necessary to reduce the size of the gel or prepare a thin fibrous gel. However, the problem has not yet been solved in terms of the method of molding the material, and a material with good temperature sensitivity has not been obtained.
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、親水性／疎水性変化、透明度変化しうる感温
性に優れた有機材料を提供することにある。Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to provide a thermosensitive material that can reversibly change its form, hydrophilicity/hydrophobicity, and transparency depending on temperature in the presence of water. Our objective is to provide organic materials with excellent properties.
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
結合が破壊され、脱水和を起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あり、系の温度を転移点より
低くすれば再度水和が起こつて水に溶解する。 By the way, polyvinyl methyl ether is hydrated with water due to hydrogen bonds at low temperatures and is water-soluble, but at temperatures above the phase transition temperature (32 to 40 degrees Celsius), the hydrogen bonds are broken, causing dehydration and releasing water. It is known that it becomes insolubilized. This phenomenon is reversible beyond the transition temperature; if the temperature of the system is lowered below the transition temperature, hydration occurs again and the substance 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、水中の疎水性有機物質を吸着、
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 have previously discovered that by utilizing the reversible changes in hydrophilicity and hydrophobicity of polyvinyl methyl ether depending on temperature, they can adsorb hydrophobic organic substances in water.
A separation method was proposed (Japanese Patent Publication No. 61-2403), but as a result of further research, it was discovered that polyvinyl methyl ether crosslinked gel reversibly swells and contracts in water depending on 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透過時間に依
存するために、前記ポリビニルメチルエーテルの
大きな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、その応答性
が著しく低い。 However, the rate of swelling and contraction of the gel due to temperature changes depends on the permeation time of water in the gel, so in the case of a large crosslinked gel of polyvinyl methyl ether, it takes several times to reach the swelling and contraction equilibrium. It takes hours to several days, and the responsiveness is extremely low.
問題点を解決するための手段
本発明者らは、ポリビニルメチルエーテルの架
橋ゲルの温度応答性が改善するために、種々研究
を重ねた結果、アニオン性高分子電解質をその水
溶性塩として混合し、次いでこれを凝固浴中で不
溶性塩に変えることによりその目的を達成しうる
ことを見出し、この知見に基づいて本発明をなす
に至つた。Means for Solving the Problems In order to improve the temperature responsiveness of cross-linked polyvinyl methyl ether gel, the present inventors have conducted various studies and found that an anionic polymer electrolyte is mixed as its water-soluble salt. Then, the inventors discovered that the object could be achieved by converting it into an insoluble salt in a coagulation bath, and based on this knowledge, the present invention was accomplished.
すなわち、本発明は、ポリビニルメチルエーテ
ル水溶液とアニオン性高分子電解質の水溶性塩の
水溶液とを混合して得たゲル調製液を、該ポリビ
ニルメチルエーテルの相転移温度以上の温度に保
持された、該アニオン性高分子電解質と不溶性の
塩を形成しうる金属の水溶性塩を含む水溶液から
成る凝固浴中に導入して、ゲルを形成させ、次い
でこのゲルを乾燥させることなく、これにガンマ
線又は電子線を照射して、ポリビニルメチルエー
テルを架橋させることを特徴とする感温性ゲルの
製造方法を提供するものである。 That is, the present invention provides a gel preparation solution obtained by mixing an aqueous solution of polyvinyl methyl ether and an aqueous solution of a water-soluble salt of an anionic polymer electrolyte, which is maintained at a temperature equal to or higher than the phase transition temperature of the polyvinyl methyl ether. A gel is formed by introducing it into a coagulation bath consisting of an aqueous solution containing a water-soluble salt of a metal capable of forming an insoluble salt with the anionic polyelectrolyte, and the gel is then exposed to gamma rays or The present invention provides a method for producing a temperature-sensitive gel, which comprises crosslinking polyvinyl methyl ether by irradiating it with an electron beam.
本発明方法においては、ポリビニルメチルエー
テルを架橋させたのち、必要に応じて酸又はアル
カリで処理して高分子電解質を除去することがで
きる。このようにして、繊維状、フイルム状、ビ
ーズ状等任意の形状の、ポリビニルメチルエーテ
ルから成る感温性ゲルを得ることができる。 In the method of the present invention, after crosslinking polyvinyl methyl ether, the polymer electrolyte can be removed by treatment with acid or alkali, if necessary. In this way, it is possible to obtain a temperature-sensitive gel made of polyvinyl methyl ether in any shape such as fibrous, film, or bead-like.
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
BF3、I2、AlCl3、FeCl3などを開始剤としてカチ
オン重合させることによつて得られる。このもの
は前述のように、水の存在下において、相転移温
度を境にして、分子の親水性／疎水性、つまり水
への溶解性が可逆的に変化する性質を有してい
る。 The polyvinyl methyl ether used in the present invention is usually methyl vinyl ether, for example
It can be obtained by cationic polymerization using BF 3 , I 2 , AlCl 3 , FeCl 3 or the like as an initiator. As described above, this material has the property that in the presence of water, the hydrophilicity/hydrophobicity of the molecule, that is, the solubility in water, changes reversibly across the phase transition temperature.
前記のように、ポリビニルメチルエーテル水溶
液の相転移温度は通常32〜40℃の範囲にあり、ポ
リビニルメチルエーテルはこの転移温度以上では
水に不溶になる。この転移温度は例えば塩化ナト
リウムや塩化カルシウムのような無機塩類を添加
することにより低下させることができる。転移点
以上で不溶化したポリビニルメチルエーテルは粘
着性を帯びており、押し出し方式では細い繊維
状、薄いフイルム状、それにビーズ状に形成する
ことができない。一方、本発明方法で用いられる
アニオン性高分子電解質としては、例えばアルギ
ン酸、ポリアクリル酸、カルボキシメチルセルロ
ースなどが挙げられる。これらのアニオン性高分
子電解質は、その水溶性塩例えばナトリウム塩の
水溶液として用いられる。 As mentioned above, the phase transition temperature of an aqueous solution of polyvinyl methyl ether is usually in the range of 32 to 40°C, and polyvinyl methyl ether becomes insoluble in water above this transition temperature. This transition temperature can be lowered by adding inorganic salts such as sodium chloride or calcium chloride. Polyvinyl methyl ether, which becomes insolubilized above its transition point, becomes sticky and cannot be formed into thin fibers, thin films, or beads by extrusion. On the other hand, examples of the anionic polymer electrolyte used in the method of the present invention include alginic acid, polyacrylic acid, and carboxymethyl cellulose. These anionic polyelectrolytes are used in the form of aqueous solutions of their water-soluble salts, such as sodium salts.
また、凝固浴中に含有させるアニオン性高分子
電解質と不溶性の塩を形成しうる金属の例として
はカルシウムやアルミニウムなどを挙げることが
でき、これは例えば塩化カルシウムやみようばん
のような水溶性塩として用いられる。 In addition, examples of metals that can form insoluble salts with the anionic polymer electrolyte contained in the coagulation bath include calcium and aluminum. used as.
本発明方法において、ポリビニルメチルエーテ
ル水溶液と、アニオン性高分子電解質の水溶性塩
の水溶液との混合物を、上記の凝固浴中に導入す
ると、アニオン性高分子電解質が、それと不溶性
の塩を形成する金属の塩と反応して水に不溶性の
ゲルを生成する。これらアニオン性高分子電解質
の不溶性ゲルは、酵素、微生物などの包埋法によ
る固定化材として用いられている本発明では、ア
ニオン性高分子電解質を包埋材として用い、ポリ
ビニルメチルエーテル水溶液とアニオン性高分子
電解質の水溶液との混合物、またポリビニルメチ
ルエーテルを芯液として、アニオン性高分子電解
質を鞘液として、アニオン性高分子電解質と不溶
性のゲルを生成する塩類の水溶液よりなる凝固浴
中に押し出し、細い繊維状、薄いフイルム状、ま
たはビーズ状のゲルを形成させることができる。
この時の凝固浴の温度は、ポリビニルメチルエー
テルが凝固浴の塩濃度にて示す転移温度以上の温
度であることがのぞましい。このようにして形成
されたゲルを乾燥させることなく、ガンマ線また
は電子線を照射することにより、該ポリビニルメ
チルエーテルを架橋させたのち、必要に応じて
酸、またはアルカリ処理を行い、アニオン性高分
子電解質を除去し、架橋ゲルを生成させる。 In the method of the present invention, when a mixture of an aqueous polyvinyl methyl ether solution and an aqueous solution of a water-soluble salt of an anionic polyelectrolyte is introduced into the above coagulation bath, the anionic polyelectrolyte forms an insoluble salt therewith. Reacts with metal salts to form a water-insoluble gel. These insoluble gels of anionic polymer electrolytes are used as immobilization materials for enzymes, microorganisms, etc. by embedding methods.In the present invention, anionic polymer electrolytes are used as embedding materials, and polyvinyl methyl ether aqueous solution and anion in a coagulation bath consisting of an aqueous solution of an anionic polyelectrolyte and an insoluble gel, with polyvinyl methyl ether as a core liquid and an anionic polyelectrolyte as a sheath liquid. The gel can be extruded and formed into fine fibers, thin films, or beads.
The temperature of the coagulation bath at this time is preferably higher than the transition temperature of polyvinyl methyl ether based on the salt concentration of the coagulation bath. Without drying the gel thus formed, the polyvinyl methyl ether is crosslinked by irradiation with gamma rays or electron beams, and then acid or alkali treatment is performed as necessary to form an anionic polymer. The electrolyte is removed and a crosslinked gel is produced.
発明の効果
本発明の感温性ゲルは、細い繊維状、薄いフイ
ルム状、そしてビーズ状であるため、従来の注型
法にて得られたゲルに比較して、形態変化、親水
性／疎水性変化、透明度変化などの温度応答性が
極めて優れており、エネルギー変換、エネルギー
貯蔵、アクチエータ、吸水材、放水材、吸着剤分
離膜、温度センサーなどへの利用が可能である。Effects of the Invention The temperature-sensitive gel of the present invention has a thin fibrous shape, a thin film shape, and a bead shape. It has excellent temperature responsiveness such as changes in properties and transparency, and can be used in energy conversion, energy storage, actuators, water absorption materials, water discharge materials, adsorbent separation membranes, temperature sensors, etc.
実施例
次ぎに実施例によつて本発明をさらに詳細に説
明する。なお各例中の部は、重量部を意味する。Examples Next, the present invention will be explained in more detail with reference to Examples. Note that parts in each example mean parts by weight.
実施例 １
ポリビニルメチルエーテルの30重量％水溶液10
部と、アルギン酸ナトリウムの４重量％水溶液２
部とを十分に混合した液を、30℃に保つた５重量
％の塩化カルシウム水溶液の凝固浴中に、直径
0.25mmのノズルを通して押し出し、繊維状に凝固
させた。この凝固したゲルを乾燥することなく、
30℃にて10メガラツドのガンマ線を照射すること
によりポリビニルメチルエーテルは架橋しゲル化
する。次ぎにこの繊維状のゲルを0.1規定の塩酸
水溶液中に浸漬し、アルギン酸カルシウムをアル
ギン酸を変え、次いで0.1規定の水酸化ナトリウ
ム水溶液中に浸漬し、アルギン酸ナトリウムとし
たのち、十分に水洗、アルギン酸を除去すること
により、細い繊維状のポリビニルメチルエーテル
の架橋ゲルを製造した。このゲルはポリビニルメ
チルエーテルと同様に37℃で相転移を起し、20℃
と40℃とでは約２倍の長さの変化を示し、温度に
より可逆的に低温では伸長、高温では収縮した。
その応答時間は10秒と短く、感温性は良好であつ
た。Example 1 30% by weight aqueous solution of polyvinyl methyl ether10
1 part and 2 parts of a 4% aqueous solution of sodium alginate
The solution with a diameter of
It was extruded through a 0.25 mm nozzle and coagulated into fibers. Without drying this solidified gel,
Polyvinyl methyl ether is crosslinked and gelled by irradiation with 10 megarads of gamma rays at 30°C. Next, this fibrous gel was immersed in a 0.1N aqueous hydrochloric acid solution to change the alginic acid to calcium alginate, then immersed in a 0.1N aqueous sodium hydroxide solution to form sodium alginate, and thoroughly washed with water to remove the alginic acid. By removing it, a thin fibrous polyvinyl methyl ether crosslinked gel was produced. This gel undergoes a phase transition at 37°C, similar to polyvinyl methyl ether, and at 20°C.
At 40°C, the length changed by about twice as much, and the length was reversible depending on the temperature, elongating at low temperatures and contracting at high temperatures.
The response time was as short as 10 seconds, and the temperature sensitivity was good.
実施例 ２
ポリビニルメチルエーテル30重量％水溶液10部
と、エーテル化度0.8のカルボキシメチルセルロ
ースナトリウムの10重量％水溶液２部とを十分に
混合した液をコーターにてガラス板上に0.3mmの
厚さにて塗布したのち、ただちに25℃に保つた10
重量％の塩化カルシウム水溶液の凝固液中に浸漬
し、フイルム状に凝固させた。次ぎにこのフイル
ム状のゲルをガラス板ごと、25℃にて直線加速器
を用い、加速電圧7MV、電子流密度29μA／９mm
φにて96秒間電子線を照射することにより、ポリ
ビニルメチルエーテルは架橋しゲル化する。次ぎ
にこのゲルの付着したガラス板を0.1規定の塩酸
水溶液中に浸漬し、カルシウムを除去したのち、
純水にて洗浄し、次いで0.1規定の水酸化ナトリ
ウム水溶液中に浸漬し、カルボキシメチルセルロ
ースをナトリウム塩にしたのち水にて十分に水
洗、カルボキシメチルセルロースを中から除去す
ることにより、厚さ0.3mmの薄いフイルム状のポ
リビニルメチルエーテルのゲルを製造した。この
フイルム状ゲルはポリビニルメチルエーテルと同
様に、37℃にて転移点を示し33℃と37℃とでは、
波長が500nｍの光の透過率が67％から４％へと
変化し、温度により可逆的に低温では透明に、高
温では不透明になる。その応答時間は約３秒であ
り、感温性は良好であつた。Example 2 A sufficiently mixed solution of 10 parts of a 30% by weight aqueous solution of polyvinyl methyl ether and 2 parts of a 10% by weight aqueous solution of sodium carboxymethylcellulose with a degree of etherification of 0.8 was coated on a glass plate with a coater to a thickness of 0.3 mm. After applying the product, immediately keep it at 25℃.
It was immersed in a coagulating solution of aqueous calcium chloride solution of % by weight to coagulate into a film. Next, this film-like gel was deposited on a glass plate using a linear accelerator at 25°C, with an acceleration voltage of 7 MV and an electron current density of 29 μA/9 mm.
By irradiating with an electron beam at φ for 96 seconds, polyvinyl methyl ether is crosslinked and gelled. Next, the glass plate with this gel attached was immersed in a 0.1N hydrochloric acid aqueous solution to remove calcium.
After washing with pure water and then immersing in a 0.1N aqueous sodium hydroxide solution to convert carboxymethylcellulose into sodium salt, the carboxymethylcellulose was thoroughly washed with water to remove the carboxymethylcellulose from inside, resulting in a 0.3mm thick fabric. A thin film-like polyvinyl methyl ether gel was produced. Like polyvinyl methyl ether, this film-like gel has a transition point at 37℃, and at 33℃ and 37℃,
The transmittance of light with a wavelength of 500 nm changes from 67% to 4%, and it becomes transparent at low temperatures and opaque at high temperatures, reversibly depending on the temperature. The response time was about 3 seconds, and the temperature sensitivity was good.
実施例 ３
ポリビニルメチルエーテルの20重量％水溶液60
部と、メチルビニルエーテル／マレイン酸ナトリ
ウム共重合体の20％水溶液40部とを十分に混合し
た液を、30℃以上の４重量％の明ばん水溶液の凝
固液中に滴下し、ビーズ状に凝固させた。このビ
ーズ状ゲルを凝固液ともに、30℃にて20メガラツ
ドのガンマ線を照射することによりポリビニルメ
チルエーテル、およびメチルビニルエーテル／マ
レイン酸共重合体を架橋し、ビーズ状のゲルが生
成される。次ぎにこのビーズ状のゲルを0.1規定
の塩酸にて洗浄し、マレイン酸と結合しているア
ルミニウムを脱離させた後、十分に水洗すること
により、ポリビニルメチルエーテル、およびポリ
ビニルメチルエーテル／マレイン酸共重合体の複
合化したビーズ状のゲルを製造した。このビーズ
状ゲルはポリビニルメチルエーテルと同様に37℃
に転移点を有し、40℃以上に加熱することによ
り、水に溶けている非イオン性界面活性剤を吸着
し、20℃以下に冷却することにより、吸着してい
た活性剤を放出する感温性良好な吸脱着作用を示
した。Example 3 20% by weight aqueous solution of polyvinyl methyl ether60
and 40 parts of a 20% aqueous solution of methyl vinyl ether/sodium maleate copolymer were dropped into a coagulating solution of a 4% alum aqueous solution at 30°C or higher, and the mixture was coagulated into beads. I let it happen. This bead-like gel is irradiated with gamma rays of 20 megarads at 30° C. to crosslink the polyvinyl methyl ether and the methyl vinyl ether/maleic acid copolymer, thereby producing a bead-like gel. Next, this bead-shaped gel is washed with 0.1N hydrochloric acid to remove aluminum bonded to maleic acid, and then thoroughly washed with water to form polyvinyl methyl ether and polyvinyl methyl ether/maleic acid. A bead-shaped gel composed of a copolymer was produced. Like polyvinyl methyl ether, this bead-like gel can be heated at 37°C.
It has a transition point at It exhibited good adsorption and desorption properties in terms of temperature.
実施例 ４
ポリビニルメチルエーテルの40重量％水溶液を
芯液とし、アルギン酸ナトリウムの５重量％水溶
液を鞘液として、芯液内径１mm、鞘液厚み0.5mm
の二重ノズルを用いて、実施例１と同様の凝固浴
を紡糸浴として湿式紡糸を行い、紡糸後ただちに
実施例２と同様の条件で電子線照射を行うことに
よりポリビニルメチルエーテルを架橋させた。次
ぎに実施例１と同様の酸、およびアルカリ処理を
行い、繊維状のポリビニルメチルエーテルの架橋
ゲルを製造した。その感温性は実施例１と同様に
良好であつた。Example 4 A 40% by weight aqueous solution of polyvinyl methyl ether was used as the core liquid, a 5% by weight aqueous solution of sodium alginate was used as the sheath liquid, the inner diameter of the core liquid was 1 mm, and the thickness of the sheath liquid was 0.5 mm.
Using a double nozzle, wet spinning was performed using the same coagulation bath as in Example 1 as a spinning bath, and immediately after spinning, polyvinyl methyl ether was crosslinked by performing electron beam irradiation under the same conditions as in Example 2. . Next, the same acid and alkali treatments as in Example 1 were performed to produce a fibrous polyvinyl methyl ether crosslinked gel. Its temperature sensitivity was as good as in Example 1.
Claims (1)
性高分子電解質の水溶性塩の水溶液とを混合して
得たゲル調製液を、該ポリビニルメチルエーテル
の相転移温度以上の温度に保持された、該アニオ
ン性高分子電解質と不溶性の塩を形成しうる金属
の水溶性塩を含む水溶液から成る凝固浴中に導入
して、ゲルを形成させ、次いでこのゲルを乾燥さ
せることなく、これにガンマ線又は電子線を照射
して、ポリビニルメチルエーテルを架橋させるこ
とを特徴とする感温性ゲルの製造方法。 ２ 二重ノズルを用い、ビニルメチルエーテル水
溶液を芯液、アニオン性高分子電解質の水溶性塩
の水溶液を鞘液として混合と同時に凝固液に導入
して湿式紡糸することにより繊維状に形成する特
許請求の範囲第１項記載の感温性ゲルの製造方
法。[Claims] 1. A gel preparation obtained by mixing an aqueous solution of polyvinyl methyl ether and an aqueous solution of a water-soluble salt of an anionic polymer electrolyte is maintained at a temperature equal to or higher than the phase transition temperature of the polyvinyl methyl ether. , into a coagulation bath consisting of an aqueous solution containing a water-soluble salt of a metal capable of forming an insoluble salt with the anionic polyelectrolyte to form a gel, which is then exposed to gamma rays without drying. Alternatively, a method for producing a temperature-sensitive gel, which comprises crosslinking polyvinyl methyl ether by irradiating it with an electron beam. 2 A patent for forming fibers by wet spinning using a double nozzle to mix an aqueous vinyl methyl ether solution as a core liquid and an aqueous solution of a water-soluble salt of an anionic polymer electrolyte as a sheath liquid into a coagulating liquid. A method for producing a temperature-sensitive gel according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16840287A JPS6434435A (en) | 1987-07-06 | 1987-07-06 | Temperature sensitive gel and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16840287A JPS6434435A (en) | 1987-07-06 | 1987-07-06 | Temperature sensitive gel and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6434435A JPS6434435A (en) | 1989-02-03 |
| JPH0547256B2 true JPH0547256B2 (en) | 1993-07-16 |
Family
ID=15867455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16840287A Granted JPS6434435A (en) | 1987-07-06 | 1987-07-06 | Temperature sensitive gel and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6434435A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2626697B2 (en) * | 1988-12-15 | 1997-07-02 | 工業技術院長 | Preparation of thermosensitive gel |
| US5534229A (en) * | 1992-09-16 | 1996-07-09 | Nomura & Shibatani | Volatilization suppressing agent |
| JPH1024223A (en) * | 1996-07-12 | 1998-01-27 | Nitto Denko Corp | Separation membrane and method for producing the same |
| JP4819984B2 (en) * | 1999-06-23 | 2011-11-24 | 独立行政法人日本原子力研究開発機構 | Self-crosslinking alkylcellulose derivatives and methods for producing them |
| AU6075799A (en) * | 1999-10-20 | 2001-04-30 | Abb Turbo Systems Ag | Method and device for cooling the flow in the radial gaps formed between rotors and stators of turbine-type machines |
| US7311861B2 (en) * | 2004-06-01 | 2007-12-25 | Boston Scientific Scimed, Inc. | Embolization |
| JP2008094951A (en) * | 2006-10-11 | 2008-04-24 | Japan Atomic Energy Agency | Production method of radiation cross-linked hydrogel |
| JP6809547B2 (en) * | 2019-02-04 | 2021-01-06 | 日清紡ホールディングス株式会社 | Hydrophobic alginic acid particle group and its production method |
| JP2021173248A (en) | 2020-04-28 | 2021-11-01 | 三菱重工業株式会社 | Turbocharger |
| CN112080028A (en) * | 2020-09-11 | 2020-12-15 | 晋江联兴反光材料有限公司 | Temperature-change waterproof reflective film |
-
1987
- 1987-07-06 JP JP16840287A patent/JPS6434435A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6434435A (en) | 1989-02-03 |
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