JPS61228009A - Production of reversibly stretchable polymer membrane - Google Patents
Production of reversibly stretchable polymer membraneInfo
- Publication number
- JPS61228009A JPS61228009A JP6808785A JP6808785A JPS61228009A JP S61228009 A JPS61228009 A JP S61228009A JP 6808785 A JP6808785 A JP 6808785A JP 6808785 A JP6808785 A JP 6808785A JP S61228009 A JPS61228009 A JP S61228009A
- Authority
- JP
- Japan
- Prior art keywords
- water
- membrane
- polymer membrane
- crosslinking agent
- methacrylic acid
- 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.)
- Pending
Links
- 229920005597 polymer membrane Polymers 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract 2
- 239000012046 mixed solvent Substances 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- 230000008602 contraction Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］ “
本発明は、医療福祉機器やロボット等の小型機械用アク
チュエータの出力媒体としての利用に適した可逆伸縮性
高分子膜の製造方法に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] “The present invention relates to a method for producing a reversibly stretchable polymer membrane suitable for use as an output medium for actuators for small machines such as medical welfare equipment and robots. It is.
［従来の技術］
従来、可逆伸縮を行う膜として、ポリメタクリル酸−ポ
リビニルアルコール共重合膜、あるいは、ポリ・Ｎ・ビ
ニルプロリドンとポリメタクリル酸を混合して水素結合
で水に不溶化した膜（特開昭５２−２８４８２号公報参
照）等が知られている。[Prior Art] Conventionally, membranes that undergo reversible expansion and contraction include polymethacrylic acid-polyvinyl alcohol copolymer membranes, or membranes made by mixing poly-N-vinylprolidone and polymethacrylic acid and making them insoluble in water through hydrogen bonding. (see Japanese Patent Laid-Open No. 52-28482), etc. are known.
しかしながら、上記従来の可逆伸縮性膜は、架橋部が短
く、剛堅の構造になっているため、弾力に乏しく、その
ためせん断応力に弱く、破断しやすいという欠点があっ
た。However, the above-mentioned conventional reversibly stretchable membrane has a short crosslinked portion and a rigid structure, so it has a drawback that it has poor elasticity, is weak against shear stress, and is easily broken.
［発明が解決しようとする問題点］
本発明の目的は、弾力性に勝れ、それによってせん断応
力に対する破壊強度が従来例に比して１０倍程度まで高
めた可逆伸縮性高分子膜の製造方法を提供することにあ
る。[Problems to be Solved by the Invention] The purpose of the present invention is to produce a reversibly stretchable polymer membrane that has excellent elasticity and has a breaking strength against shear stress that is approximately 10 times higher than that of conventional examples. The purpose is to provide a method.
［問題点を解決するための手段］
上記目的を達成するため、本発明の方法は、メタクリル
酸モノマーと（ＣＨ，＝ＣＲ−Ｃｏ） ２Ｘ型の架橋剤
（ＲはＨまたはアルキル基、Ｘは−Ｎ ＨＣＨ２Ｎ Ｈ
−または−ＱＣ２Ｈ，Ｏ−）とを、水いは水・エタノー
ル混合溶媒中で混合し、それを重合させて膜を形成する
ことを特徴とするものである。[Means for Solving the Problems] In order to achieve the above object, the method of the present invention combines a methacrylic acid monomer and a (CH,=CR-Co) 2X type crosslinking agent (R is H or an alkyl group, X is a -NHCH2NH
- or -QC2H,O-) in water or a mixed solvent of water and ethanol, and the mixture is polymerized to form a film.
以下に本発明の方法についてさらに詳細に説明する。The method of the present invention will be explained in more detail below.
本発明による可逆伸縮性高分子膜の製造に際しては、上
述したように、メタクリル酸モノマーと柔軟性を有する
架橋剤とを水または水Φエタノール混合溶媒中で混合し
、それを重合させる。In producing a reversibly stretchable polymer membrane according to the present invention, as described above, a methacrylic acid monomer and a flexible crosslinking agent are mixed in water or a mixed solvent of water and Φethanol, and the mixture is polymerized.
上記架橋剤としては、ビスアクリルアミド等の（ＣＨ２
＝ＣＲ−Ｃｏ） ２Ｘ型のものが用いられ、その架橋剤
におけるＲは、ＨまたはＣＨ，またはＣ２Ｆ４等ノアル
キル基、Ｘは−Ｎ ＨＣＨ２Ｎ Ｈ−または−ＱＣ，Ｈ
，Ｏ−などとすることができる。As the crosslinking agent, (CH2
=CR-Co) 2X type is used, R in the crosslinking agent is H or CH, or a noalkyl group such as C2F4, and X is -N HCH2N H- or -QC, H
, O-, etc.
上記メタクリル酸と架橋剤の混合比（モル比）は、１０
〜１００とするのが適切である０モル比を上記範囲より
も低い値とした場合には透明な膜は形成されず、また上
記範囲よりも高い値とした場合には、形成される膜の弾
力が非常に大きくなるものの１強度的に弱く、実用に耐
えないものとなる。従って、どのような特性の膜を製造
するかによって上記モル比を決定することになり、例え
ば弾力を重視する場合には、上記範囲の中で高い値を選
び２強度を重視する場合には低い値を選べばよい。The mixing ratio (mole ratio) of the above methacrylic acid and crosslinking agent is 10
If the 0 molar ratio, which is appropriately set to 100, is set to a value lower than the above range, a transparent film will not be formed, and if the value is set higher than the above range, the formed film will not be formed. Although the elasticity is very high, the strength is weak and cannot be put to practical use. Therefore, the above molar ratio is determined depending on the characteristics of the film to be manufactured. For example, if elasticity is important, choose a high value within the above range; 2) If strength is important, choose a low value. Just choose the value.
このようにして混合したメタクリル酸と架橋剤とは、過
硫酸アンモニウムその他の適宜開始剤の作用により重合
させ、高分子膜が形成される。上記重合は、柔軟性を有
する上記架橋剤で共有結合により架橋することによって
行われ、そのため結合エネルギーが水素結合や疎水結合
に比して一桁大きくなり、高分子膜は弾力に勝れ、従来
の可逆伸縮性高分子膜に比べ、せん断応力に対する破壊
強度で１０倍程度優れている。そのため、膜を支持する
治具との連結部で裂けにくいという特徴を有している。The methacrylic acid and crosslinking agent thus mixed are polymerized by the action of ammonium persulfate or other appropriate initiator to form a polymer film. The above polymerization is carried out by covalent cross-linking with the flexible cross-linking agent, and as a result, the bond energy is an order of magnitude larger than that of hydrogen bonds or hydrophobic bonds, and the polymer membrane has better elasticity than conventional Compared to reversibly stretchable polymer membranes, it has about 10 times better fracture strength against shear stress. Therefore, it has the characteristic that it is difficult to tear at the connection part with the jig that supports the membrane.
さらに、重合条件によって弾性率を１０〜１００００
ｋｇ／ｃｒｎ’の範囲で変えることができ、膜のある部
分を硬めに、他のＢ部分をやわらかめにするなど、自在
に作成することができ、金属性治具等硬い材料との適合
性を高めることができる。Furthermore, depending on the polymerization conditions, the elastic modulus can be adjusted to 10 to 10,000.
It can be changed within the range of kg/crn', and can be made freely such as making some parts of the membrane harder and other parts B softer, and is compatible with hard materials such as metal jigs. can be increased.
上記方法で作られた高分子膜は、それを浸す溶液の成分
を変えることにより、自在にその寸法を変えることがで
き、変形に伴ってカを発生させることができる。The dimensions of the polymer membrane made by the above method can be changed freely by changing the components of the solution in which it is immersed, and force can be generated as the membrane is deformed.
例えば、高分子膜を厚さ０．２ｍｍ、幅２〜３■及び長
さ２ｃｍのテープ状のものとし、その一端に１ｇの重り
をつけた状態で水酸化ナトリウム ０．５モルあるいは
塩酸０．５モルの溶液中に入れて、長さを変化させるこ
とができ、また上記高分子膜を溶液中に入れ、その溶液
のｐｎをＰＨＩ−ＰＨ５の範囲で変化させることにより
、５０パーセント近く伸縮させることができた。このよ
うな高分子膜は、可逆的に化学会機械エネルギー交換を
行う高分子材料として、新型軽量アクチュエータの出力
媒体等に利用することができる。For example, a polymer film is made into a tape with a thickness of 0.2 mm, a width of 2 to 3 cm, and a length of 2 cm, and with a 1 g weight attached to one end, 0.5 mol of sodium hydroxide or 0.5 mol of hydrochloric acid is added. The length can be changed by placing it in a 5 mol solution, and by placing the above polymer membrane in a solution and changing the pn of the solution in the range of PHI-PH5, it can be expanded and contracted by nearly 50%. I was able to do that. Such a polymer film can be used as an output medium of a new type of lightweight actuator as a polymer material that performs reversible mechanical energy exchange.
［実施例］ 以下に本発明の実施例について説明する。[Example] Examples of the present invention will be described below.
１亙１」
精製水 ４．７１ｇメタ
クリル酸 ０．９θｇＮＮ’
メチレンビスアクリルアミド ０．１１ｇ上記３成分
を良く混合し、重合開始剤として過硫酸アンモニウムを
小スパーチルに半さじ（耳かき半分）程度混入し、よく
攪拌した。それを内径５８ｍｍのガラス製シャーレに５
ｇ入れ、５０℃で約５０Ｔｏｒｒに減圧し重合させた０
反応時間としては、４時間〜６時間を必要とした。Purified water 4.71g Methacrylic acid 0.9θgNN'
Methylenebisacrylamide 0.11g The above three components were mixed well, and about half a teaspoon (half an earpick) of ammonium persulfate as a polymerization initiator was mixed into a small spatula, followed by thorough stirring. Place it in a glass petri dish with an inner diameter of 58 mm.
g, and polymerized by reducing the pressure to about 50 Torr at 50°C.
The reaction time required 4 to 6 hours.
第１図は上記重合に使用した減圧恒温装置を示し、１は
恒温器、２は減圧容器、３はガラス製シャーレ、４は真
空ポンプである。なお、５は上記シャーレ３に入れた３
成分混合液を示す。FIG. 1 shows a vacuum constant temperature apparatus used for the above polymerization, in which 1 is a constant temperature chamber, 2 is a vacuum container, 3 is a glass petri dish, and 4 is a vacuum pump. In addition, 5 is the 3 that was placed in the petri dish 3 above.
The component mixture is shown.
その結果、透明な厚さ０．２〜０．３１の高分子膜が得
られた。これを水に浸し膨潤させることにより、シャー
レの底から剥離して使用に供することができた。As a result, a transparent polymer film having a thickness of 0.2 to 0.31 mm was obtained. By soaking it in water and allowing it to swell, it could be peeled off from the bottom of the petri dish and used.
！」Ｌ九ヱ
精製水 １．３３ｇエタ
ノール ｏ、ｅｅｇメタク
リル酸 ３．００ｇＮＮ’ メ
チレンビスアクリルアミド ０．１０ｇ上記４成分を
よく混合し、重合開始剤を実施例１と同じく添加してよ
く混合し、試験管に入れた。その中に、２本のガラス管
をアルミホイールのスペーサを使って同軸に固定し、液
を両管の隙間に満たした。それを減圧容器に入れ、空気
を抜き、代りに窒素ガスを封入し、６０℃の恒温器の中
で１５時間はど保持した、そうすると、同軸管の隙間に
チューブ状の膜が形成された。外管を割って中のチュー
ブを露出させ、水に浸してチューブを膨潤させ、内管か
ら抜取ることにより、チューブ状の高分子膜を得ること
ができた。! "L9E Purified water 1.33 g Ethanol o, eeg Methacrylic acid 3.00 g NN' Methylenebisacrylamide 0.10 g The above four components were mixed well, and a polymerization initiator was added in the same manner as in Example 1, mixed well, and tested. I put it in a tube. Inside, two glass tubes were coaxially fixed using aluminum wheel spacers, and the gap between the tubes was filled with liquid. It was placed in a vacuum container, the air was removed, nitrogen gas was filled in, and the container was kept in a thermostat at 60°C for 15 hours. As a result, a tube-shaped film was formed in the gap between the coaxial tubes. By splitting the outer tube to expose the inner tube, soaking it in water to swell it, and pulling it out from the inner tube, a tubular polymer membrane could be obtained.
［発明の効果］
このように本発明によれば、すぐれた強度を保持し、弾
力性にも勝れた高分子膜を極めて容易に得ることができ
る。[Effects of the Invention] As described above, according to the present invention, a polymer membrane that maintains excellent strength and has excellent elasticity can be obtained extremely easily.
第１図は本発明の実施に使用した装置の構成図である。 FIG. 1 is a block diagram of an apparatus used to implement the present invention.
Claims (1)
＿２Ｘ型の架橋剤（ＲはＨまたはアルキル基、Ｘは−Ｎ
ＨＣＨ＿２ＮＨ−または−ＯＣ＿２Ｈ＿４Ｏ−）とを、
水あるいは水・エタノール混合溶媒中で混合し、それを
重合させて膜を形成することを特徴とする可逆伸縮性高
分子膜の製造方法。1. Methacrylic acid monomer and (CH_2=CR-CO)
_2X type crosslinking agent (R is H or an alkyl group, X is -N
HCH_2NH- or -OC_2H_4O-),
A method for producing a reversibly stretchable polymer membrane, which comprises mixing in water or a mixed solvent of water and ethanol and polymerizing the mixture to form a membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6808785A JPS61228009A (en) | 1985-03-30 | 1985-03-30 | Production of reversibly stretchable polymer membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6808785A JPS61228009A (en) | 1985-03-30 | 1985-03-30 | Production of reversibly stretchable polymer membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61228009A true JPS61228009A (en) | 1986-10-11 |
Family
ID=13363600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6808785A Pending JPS61228009A (en) | 1985-03-30 | 1985-03-30 | Production of reversibly stretchable polymer membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61228009A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5342285A (en) * | 1976-09-29 | 1978-04-17 | Wako Pure Chem Ind Ltd | Preparation of crosslinked polymer from carboxyl type monomer |
| JPS5672005A (en) * | 1979-11-19 | 1981-06-16 | Sumitomo Chem Co Ltd | Production of polymeric material having high water absorptivity |
| JPS56147809A (en) * | 1980-04-18 | 1981-11-17 | Sumitomo Chem Co Ltd | Highly water absorbing hydrogel and its preparation |
-
1985
- 1985-03-30 JP JP6808785A patent/JPS61228009A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5342285A (en) * | 1976-09-29 | 1978-04-17 | Wako Pure Chem Ind Ltd | Preparation of crosslinked polymer from carboxyl type monomer |
| JPS5672005A (en) * | 1979-11-19 | 1981-06-16 | Sumitomo Chem Co Ltd | Production of polymeric material having high water absorptivity |
| JPS56147809A (en) * | 1980-04-18 | 1981-11-17 | Sumitomo Chem Co Ltd | Highly water absorbing hydrogel and its preparation |
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