JPS62101637A - Porous membrane rendered ion-exchangeable - Google Patents
Porous membrane rendered ion-exchangeableInfo
- Publication number
- JPS62101637A JPS62101637A JP60241606A JP24160685A JPS62101637A JP S62101637 A JPS62101637 A JP S62101637A JP 60241606 A JP60241606 A JP 60241606A JP 24160685 A JP24160685 A JP 24160685A JP S62101637 A JPS62101637 A JP S62101637A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- substance
- porous membrane
- ion
- pore
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 238000005342 ion exchange Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000004898 kneading Methods 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 238000005341 cation exchange Methods 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 abstract description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 2
- 150000001768 cations Chemical class 0.000 abstract 2
- 238000003490 calendering Methods 0.000 abstract 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003014 ion exchange membrane Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008206 lipophilic material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Landscapes
- Manufacture 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】
Ａ産業上の利用分野
本発明は、電気化学工業の分野で広く利用することの可
能なイオン交換性を有する多孔質膜に関するものである
。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a porous membrane having ion exchange properties that can be widely used in the field of electrochemical industry.
Ｂ発明の概要
この発明は、化学工業、電解工業あるいは電池などに広
く使用されている多孔質膜にイオン交換性を付与したも
ので、多機能性イオン交換膜を提供しようとするもので
ある。B. Summary of the Invention The present invention is a porous membrane widely used in the chemical industry, electrolytic industry, batteries, etc., which is provided with ion exchange properties, and is intended to provide a multifunctional ion exchange membrane.
Ｃ従来の技術
本体が微細な多孔質構造である膜は、従来から化学工業
、電解工業、醸造工業その他で広く使用されている。C. Conventional Technology Membranes having a fine porous structure have been widely used in the chemical industry, electrolysis industry, brewing industry, and other industries.
特に、電解工業や電池の分野では、イオンの移動に特徴
を有していることから、それぞれの分野にマツチした各
種の提案がなされている。In particular, in the fields of electrolytic industry and batteries, various proposals have been made that are suitable for the respective fields because of the characteristics of ion movement.
これら従来に使用されている多孔質膜は、膜自体の厚さ
、開口の密度、孔径の大きさなどを制御することにより
必要とする目的の効果をえているものである。These conventionally used porous membranes achieve the desired effect by controlling the thickness of the membrane itself, the density of the openings, the size of the pores, etc.
一方、このような多孔質膜とは別に、いわゆるイオン交
換性膜も上に述べた分野で使用されるようにな９、最近
では多孔性とイオン交換性を同時に有する多機能性膜も
提案されている。On the other hand, apart from such porous membranes, so-called ion-exchange membranes are also used in the fields mentioned above9, and recently, multifunctional membranes that have both porosity and ion-exchange properties have also been proposed. ing.
このような膜は、多孔質膜の片面あるいは両面に物理的
手段、あるいは化学的手段を用いてイオン交換性膜を設
ける方法が採られているのが普通である。Such membranes generally employ a method of providing an ion exchange membrane on one or both sides of a porous membrane using physical or chemical means.
Ｄ発明が解決しようとする問題点
このような従来の多機能性膜の場合には、全体として膜
の厚さが厚くなり、電気抵抗の観点からみても常に高め
のものとなってしまうという欠点を有するものであった
。D Problems to be solved by the invention In the case of such conventional multifunctional films, the overall thickness of the film is large, and the disadvantage is that it is always high from the viewpoint of electrical resistance. It had a
別の観点から述べると、イオン交換性膜は、多孔質膜と
は異なり本来的に膜中のイオン移動抵抗が大きいため、
上述のように多孔質膜に物理的手段、あるいは化学的手
段を用いて単に付与した多層構造のものであるときは、
電気抵抗の小さいものは本質的に得られにくい。From another perspective, unlike porous membranes, ion-exchange membranes inherently have a high resistance to ion movement within the membrane;
As mentioned above, when it has a multilayer structure simply applied to a porous membrane using physical means or chemical means,
Materials with low electrical resistance are essentially difficult to obtain.
さらに、イオン交換膜は、極めて高価なものであること
から、本来的に有効な機能を有しているものでありなが
ら、一般には広く用いられていないのが現状であった。Furthermore, since ion exchange membranes are extremely expensive, they have not been widely used, even though they inherently have effective functions.
Ｅ問題点を解決するための手段
本発明は、このような周囲の状況に鑑み種々検討を行い
到達したものであって、高分子化合物からなる母体物質
とイオン交換性物質および多孔質形成物質を混練した後
に成膜し、ついで多孔質形成物質を膜中から取り除くこ
とからなるイオン交換性を付与した多孔質膜に関するも
のである。E Means for Solving Problems The present invention has been achieved through various studies in view of the surrounding circumstances, and is based on the following: The present invention relates to a porous membrane provided with ion exchange properties, which is formed by kneading, forming a membrane, and then removing a pore-forming substance from the membrane.
Ｆ作 用
本発明において述べる高分子化合物からなる母体物質と
は、ポリオレフィン系樹脂、ポリアミド系樹脂、ポリイ
ミド系樹脂、その他同様な機能を示す合成樹脂を使用す
ることができるが、安価でしかも入手が容易であるとい
う観点からみれば最も一般的にはポリオレフィン樹脂中
のポリエチレンを使用すると便利である。F action The base substance made of a polymer compound described in the present invention can be a polyolefin resin, a polyamide resin, a polyimide resin, or other synthetic resins that exhibit similar functions. From the standpoint of ease, it is most commonly convenient to use polyethylene in polyolefin resins.
このものは、例えば電池に使用するときには、耐薬品性
を強く要求されるが、この要求に十分に応えることがで
きるものである。When this material is used, for example, in batteries, chemical resistance is strongly required, and this material can fully meet this requirement.
一方のイオン交換性物質ζよ、高分子系のものとしてス
チレンとジビニルベンゼンとの共重合体を使用するのが
最も一般的であるが、そのほか例えば近年開発されてき
ているポリビニルアルコールを母体としたイオン交換樹
脂などを使用することもできる。On the other hand, as for ion exchange material ζ, the most common polymer is a copolymer of styrene and divinylbenzene. Ion exchange resins and the like can also be used.
高分子化合物からなる母体物質とイオン交換性物質との
使用比率は、前者１００重量部に対して後者を１０〜１
１０重量部とすることが好ましい。The ratio of the base material consisting of a polymer compound and the ion exchange material is 10 to 1 parts by weight of the latter to 100 parts by weight of the former.
The amount is preferably 10 parts by weight.
イオン交換性物質の使用量が前記の１０重量部より少な
くなると十分な効果を発揮させることができないし、一
方１１０重量部より多くなると膜の強度の観点から不都
合が起こり易くなる。If the amount of the ion-exchangeable substance used is less than 10 parts by weight, sufficient effects cannot be exhibited, while if it is more than 110 parts by weight, problems tend to occur from the viewpoint of membrane strength.
なお、特に多孔質膜のイオン交換能力（一般的には、こ
れをイオン交換容量とよんでいる）を向上させる必要が
あるときなどの場合には、必要に応じて目的とする特性
が付与されるように１１０重量部以上の比率範囲のなか
から使用することが可能なのはいうまでもない。Note that, especially when it is necessary to improve the ion exchange capacity (generally referred to as ion exchange capacity) of a porous membrane, the desired characteristics may be imparted as necessary. Needless to say, it is possible to use a proportion within the range of 110 parts by weight or more.
高分子化合物からなる母体物質に多孔性を与えるものと
しては親油性のものと親水性のものがある。There are lipophilic materials and hydrophilic materials that impart porosity to a matrix material made of a polymer compound.
そのうち、親油性のタイプのものとしては石油オイル、
ジオクチルフタレートなどがあり、また親水性のものに
はポリビニルアルコールや塩化カリ、塩化ナトリウム等
の無機塩を使用することができる。Among these, the lipophilic types include petroleum oil,
Examples include dioctyl phthalate, and hydrophilic ones include polyvinyl alcohol and inorganic salts such as potassium chloride and sodium chloride.
これらの多孔性をあたえる物質は、高分子化合物１００
重量部に対し２０〜１４０重量部の範囲で使用すること
が好ましい。The substance that provides these porosity is a polymer compound 100
It is preferable to use it in a range of 20 to 140 parts by weight.
使用量が２０重量部より少ないときには、当然のことな
がら開口率は少なくなり、膜を構成する材料を均一に濡
らすことが難しくなると共に多孔質膜中のイオンの流通
が十分でなくなる。When the amount used is less than 20 parts by weight, the aperture ratio naturally decreases, making it difficult to uniformly wet the material constituting the membrane and making it difficult for ions to flow through the porous membrane.
また逆に１４０重量部を超えると成形加工性に問題を生
じ、特に１５０重量部以上の使用量となるときは膜自体
の機械的強度が極端に低下する結果を招来する。On the other hand, if the amount exceeds 140 parts by weight, problems will occur in molding processability, and especially if the amount used exceeds 150 parts by weight, the mechanical strength of the membrane itself will be extremely reduced.
Ｇ実施例
以下、具体的な例に基づいて本発明の構成および効果を
説明する。G Example Hereinafter, the structure and effects of the present invention will be explained based on a specific example.
密度０．９６ｇ／ｃｊ、ＭＦＲｏ、８０ｇ／１０ｗ１ｎ
のポリエチレン１００重量部に対して、平均長さ５０μ
ｍ、平均長径３０μｍ１平均短径１０μｍのイオン交換
樹脂粉末にチビ製、イオン交換容量３，６ｍｅｑ／ｇ）
を５０１ｉ量部添加して均一混合した。Density 0.96g/cj, MFRo, 80g/10w1n
The average length is 50μ per 100 parts by weight of polyethylene.
m, average major axis 30 μm 1 average minor axis 10 μm ion exchange resin powder manufactured by Chibi, ion exchange capacity 3.6 meq/g)
501 parts of were added and mixed uniformly.
この混合物にジオクチルフタレートをｉｏｏｇ量部加え
、バンバリーミキサ−により混練した。An ioog amount of dioctyl phthalate was added to this mixture, and the mixture was kneaded using a Banbury mixer.
その後、カレンダー成形機により厚さ１謹の膜に成形し
、トリクロルエチレンを抽出剤として用い膜中のジオク
チルフタレートを抽出除去した。Thereafter, it was formed into a membrane with a thickness of 1 100 mm using a calendar molding machine, and dioctyl phthalate in the membrane was extracted and removed using trichlorethylene as an extractant.
このようにして得たイオン交換性多孔質膜は、比表面積
が３００ｃｄ／ｇで、イオン交換容量の値が０．９ 醜
ｅｑ／ ｇであることを確認した。It was confirmed that the ion exchange porous membrane thus obtained had a specific surface area of 300 cd/g and an ion exchange capacity of 0.9 eq/g.
さらに、上記イオン交換粉末を１００重量部に増加し、
その他は同一条件として得たイオン交換性多孔質膜は、
比表面積が４７０ｃｊ／ｇで、イオン交換容量の値は、
１．４ ｍｅｑ／ ｇであった。Furthermore, the ion exchange powder was increased to 100 parts by weight,
The ion-exchange porous membrane obtained under otherwise the same conditions was
The specific surface area is 470cj/g, and the ion exchange capacity is:
It was 1.4 meq/g.
Ｈ発明の効果
本発明に従うと、比較的簡単な製造工程で製造すること
ができるにかかわらず所望の性能のイオン交換性多孔質
膜を自在に得ることが可能であり、各種の製造工業、装
置工業において有用なものとなるものである。H Effects of the Invention According to the present invention, it is possible to freely obtain an ion-exchange porous membrane with desired performance even though it can be manufactured through a relatively simple manufacturing process, and it can be used in various manufacturing industries and devices. It will be useful in industry.
Claims (4)
質および多孔質形成物質を混練した後に成膜し、ついで
多孔質形成物質を膜中から取り除くことからなるイオン
交換性を付与した多孔質膜。(1) A porous membrane with ion exchange properties that is formed by kneading a base material made of a polymer compound, an ion exchange material, and a porosity forming substance, and then removing the porosity forming substance from the membrane. .
末１０〜１１０重量部を混練し成形することからなるこ
とからなる特許請求の範囲第１項に記載の多孔質膜。(2) The porous membrane according to claim 1, which is obtained by kneading 10 to 110 parts by weight of a powder having ion-exchange properties with 100 parts by weight of a base substance and molding the mixture.
を有する粉末を使用することからなる特許請求の範囲第
１項に記載の多孔質膜。(3) The porous membrane according to claim 1, which uses a powder having cationic, anionic, or amphoteric functions.
陽イオン交換基あるいは−Ｎ＾＋（ＣＨ＿３）＿３、−
Ｎ＾＋Ｈ＿３の陰イオン交換基のなかから選ばれたこと
からなる特許請求の範囲第１項に記載の多孔質膜。(4) Cation exchange group where the ion exchange group is -SO_3^-, -COO^- or -N^+(CH_3)_3, -
The porous membrane according to claim 1, which is selected from among the anion exchange groups N^+H_3.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60241606A JPS62101637A (en) | 1985-10-30 | 1985-10-30 | Porous membrane rendered ion-exchangeable |
| US06/922,709 US4824743A (en) | 1985-10-30 | 1986-10-24 | Secondary battery with ion-exchange porous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60241606A JPS62101637A (en) | 1985-10-30 | 1985-10-30 | Porous membrane rendered ion-exchangeable |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62101637A true JPS62101637A (en) | 1987-05-12 |
Family
ID=17076816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60241606A Pending JPS62101637A (en) | 1985-10-30 | 1985-10-30 | Porous membrane rendered ion-exchangeable |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62101637A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010106347A (en) * | 2008-10-31 | 2010-05-13 | Japan Organo Co Ltd | Electrode member and electrolytic apparatus |
| WO2014119208A1 (en) * | 2013-01-31 | 2014-08-07 | 日東電工株式会社 | Electrolytic membrane |
| WO2014119207A1 (en) * | 2013-01-31 | 2014-08-07 | 日東電工株式会社 | Electrolytic membrane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4938429A (en) * | 1972-08-15 | 1974-04-10 |
-
1985
- 1985-10-30 JP JP60241606A patent/JPS62101637A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4938429A (en) * | 1972-08-15 | 1974-04-10 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010106347A (en) * | 2008-10-31 | 2010-05-13 | Japan Organo Co Ltd | Electrode member and electrolytic apparatus |
| WO2014119208A1 (en) * | 2013-01-31 | 2014-08-07 | 日東電工株式会社 | Electrolytic membrane |
| WO2014119207A1 (en) * | 2013-01-31 | 2014-08-07 | 日東電工株式会社 | Electrolytic membrane |
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