JP3218090B2 - Manufacturing method of polymer electrolyte composite - Google Patents
Manufacturing method of polymer electrolyte compositeInfo
- Publication number
- JP3218090B2 JP3218090B2 JP20804392A JP20804392A JP3218090B2 JP 3218090 B2 JP3218090 B2 JP 3218090B2 JP 20804392 A JP20804392 A JP 20804392A JP 20804392 A JP20804392 A JP 20804392A JP 3218090 B2 JP3218090 B2 JP 3218090B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- polymer electrolyte
- electrolyte composite
- graft
- group
- 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 - Fee Related
Links
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、放射線グラフト共重合
による産業上有用な高分子電解質複合体の製造法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an industrially useful polymer electrolyte composite by radiation graft copolymerization.
【０００２】[0002]
【従来の技術】高分子電解質複合体は、ポリイオンコン
プレックスとも呼ばれ、ポリカチオンとポリアニオンと
をイオン架橋によって会合せしめゲル化を図ったもので
ある。2. Description of the Related Art A polyelectrolyte complex, also called a polyion complex, is one in which a polycation and a polyanion are associated by ionic crosslinking to form a gel.
【０００３】実際的な面から応用が広く試みられている
ものに、ポリスチレンスルホン酸塩とポリビニルベンジ
ルトリメチルアンモニウム塩から形成されるポリイオン
コンプレックスがある。これは両成分の希薄溶液を混合
することによって得られ、水／極性溶媒／低分子塩の３
成分溶媒系を用いたキャスト法によりフィルムに、そし
て浸漬キャスト法により他の材料にコーティングされ
る。また、粒状ポリビニルベンジルトリメチルアンモニ
ウムクロリド樹脂へスチレンスルホン酸ナトリウムを浸
漬させた後、重合させることによっても得られ、スネー
クケージ樹脂として用いられる。[0003] A polyion complex formed from a polystyrenesulfonate and a polyvinylbenzyltrimethylammonium salt has been widely attempted from a practical point of view. This is obtained by mixing a dilute solution of both components, resulting in a water / polar solvent / low molecular weight salt.
The film is coated by the casting method using the component solvent system, and the other material is coated by the immersion casting method. It is also obtained by immersing sodium styrenesulfonate in granular polyvinylbenzyltrimethylammonium chloride resin, followed by polymerization, and used as a snake cage resin.
【０００４】しかし、これらポリイオンコンプレックス
は、耐熱性が悪い、乾燥した状態では柔軟性に乏しく堅
く脆いなど物理的性質に問題がある。また、織布、不織
布等へのコーティングでは、その空隙部が埋められてし
まい、その基材の特性を十分に生かせない場合も考えら
れる。However, these polyion complexes have problems in physical properties such as poor heat resistance and poor rigidity and brittleness in a dry state. Further, in the case of coating a woven fabric, a nonwoven fabric, or the like, the voids may be filled, and the characteristics of the base material may not be fully utilized.
【０００５】以上のような物理的性質や加工性の問題を
解決するために、織布、不織布、ネット等へ成型加工し
た基材へスチレン、クロロメチルスチレン、ビニルベン
ジルジアルキルアミン等を放射線グラフト重合した後、
四級アンモニウム基、スルホン基を導入することが考え
られるが、官能基導入にともなう副反応の発生や官能基
量の制御など困難である。In order to solve the problems of physical properties and workability as described above, styrene, chloromethylstyrene, vinylbenzyldialkylamine and the like are radiation-grafted onto a base material formed into a woven fabric, a nonwoven fabric, a net, or the like. After doing
It is conceivable to introduce a quaternary ammonium group or a sulfone group, but it is difficult to control the amount of a functional group or the occurrence of a side reaction accompanying the functional group.
【０００６】[0006]
【発明が解決しようとする課題】物理的性質に優れ、用
途に適した形状へ成型加工の容易な、高分子電解質複合
体の製造法。SUMMARY OF THE INVENTION A method for producing a polymer electrolyte composite which has excellent physical properties and is easy to mold into a shape suitable for use.
【０００７】[0007]
【課題を解決するための手段】本発明は、前項に記した
要件を満たす高分子電解質複合体の製造法として、成型
加工した有機重合体に電離性放射線を照射した後、カチ
オン基を持つモノマーそしてアニオン基を持つモノマー
のグラフト共重合を用いて、カチオン基とアニオン基を
導入したことを特徴とする高分子電解質複合体の製造法
を解決手段として提供するものである。According to the present invention, there is provided a method for producing a polymer electrolyte composite satisfying the requirements described in the preceding paragraph, wherein a molded organic polymer is irradiated with ionizing radiation and then a monomer having a cationic group is irradiated. The present invention also provides, as a solution, a method for producing a polymer electrolyte composite, wherein a cationic group and an anionic group are introduced by using graft copolymerization of a monomer having an anionic group.
【０００８】本発明に用いる基材の材質としては、ポリ
エチレン、ポリプロピレンなどのポリオレフィンや、ハ
ロゲン化ポリオレフィン系のものが好適であるが、これ
らに限定されるものではない。放射線グラフト重合は、
基材の形状を比較的自由に選択できるので、用途に適し
た形状の基材を選ぶことができる。The material of the substrate used in the present invention is preferably a polyolefin such as polyethylene or polypropylene, or a halogenated polyolefin-based material, but is not limited thereto. Radiation graft polymerization is
Since the shape of the substrate can be selected relatively freely, a substrate having a shape suitable for the application can be selected.
【０００９】ここで放射線グラフト重合に用いられる電
離性放射線は、α、β、γ線、電子線、紫外線などがあ
り、いずれも使用可能であるが、γ線や電子線などが本
発明に適している。照射線量は基材によって異なるが、
５０ｋＧｙ〜３００ｋＧｙ、好ましくは１００ｋＧｙ〜
２００ｋＧｙである。過少な照射では、必要なグラフト
重合に十分なラジカルの生成量が得られず、過剰な照射
は、不経済であるばかりか、基材の不必要な架橋や、部
分的な分解によってグラフト重合を妨げることがある。The ionizing radiation used in the radiation graft polymerization includes α, β, γ-rays, electron beams and ultraviolet rays, and any of them can be used, but γ-rays and electron beams are suitable for the present invention. ing. The irradiation dose varies depending on the base material,
50 kGy to 300 kGy, preferably 100 kGy
200 kGy. Insufficient irradiation does not provide enough radicals for the required graft polymerization.Excessive irradiation is not only uneconomical, but also leads to unnecessary cross-linking and partial decomposition of the base material. May hinder.
【００１０】基材に放射線を照射する方法としては、基
材とモノマーの共存下に放射線を照射する同時照射法
と、予め基材を照射した後、モノマーと接触させる前照
射法があるが、モノマーの単独重合物の生成の少ない前
照射法の方が有利である。As a method of irradiating the substrate with radiation, there are a simultaneous irradiation method of irradiating radiation in the presence of the substrate and the monomer, and a pre-irradiation method of irradiating the substrate in advance and then contacting with the monomer. The pre-irradiation method in which formation of a homopolymer of a monomer is small is more advantageous.
【００１１】本発明で使用するモノマーは、カチオン基
を持つモノマーとしてビニルベンジルトリメチルアンモ
ニウム塩が、アニオン基を持つモノマーとしてスチレン
スルホン酸塩が用いられるが、これらに限定されるもの
ではない。As the monomer used in the present invention, vinylbenzyltrimethylammonium salt is used as a monomer having a cationic group, and styrene sulfonate is used as a monomer having an anionic group, but is not limited thereto.
【００１２】あらかじめ照射を受けた基材へのグラフト
重合は、基材とモノマー溶液とを無酸素下、液相で接触
させるだけでよい。The graft polymerization onto the substrate which has been irradiated in advance may be carried out simply by bringing the substrate and the monomer solution into contact with each other in a liquid phase under oxygen-free conditions.
【００１３】モノマー溶液との接触時間は、基材や照射
線量により異なるが、３時間〜５時間で十分なグラフト
重合体が得られる。また、照射した基材に、ＳＳＳとＱ
Ｂｍ以外のモノマーを気相あるいは、含浸グラフト重合
した後でも、そのグラフト体に十分なラジカルが残って
いれば、続けてＳＳＳとＱＢｍモノマーと反応させるこ
とができる。Although the contact time with the monomer solution varies depending on the substrate and the irradiation dose, a sufficient graft polymer can be obtained in 3 to 5 hours. In addition, SSS and Q
Even after a monomer other than Bm is vapor-phased or impregnated by graft polymerization, if sufficient radicals remain in the graft, SSS and the QBm monomer can be continuously reacted.
【００１４】反応温度は、３０℃〜８０℃、好ましくは
５０℃〜７０℃である。[0014] The reaction temperature is 30 ° C to 80 ° C, preferably 50 ° C to 70 ° C.
【００１５】本発明の利点は、種々の形状に成型加工し
た有機重合体へ放射線前照射グラフト重合するだけでカ
チオン基とアニオン基を導入でき物理的性質に優れた高
分子電解質複合体が得られる点である。An advantage of the present invention is that a polymer electrolyte composite having excellent physical properties can be obtained by introducing cation groups and anion groups only by graft irradiation polymerization pre-radiation onto an organic polymer molded and processed into various shapes. Is a point.
【００１６】[0016]
【実施例】以下に本発明による製造法の実施例を説明す
る。Examples of the production method according to the present invention will be described below.
【００１７】[0017]
【実施例１】繊維径４０μｍのポリプロピレン製繊維よ
りなる不織布（倉敷繊維加工社製：ＣＦ−ＩＩＩ）に電
子線加速器を用いて、２００ｋＧｙを照射した後、予め
脱酸素したスチレンスルホン酸ナトリウム、トリメチル
ビニルベンジルアンモニウム塩及びアクリル酸の三成分
混合３６％水溶液中、５０℃で２時間３０分反応させ、
６１％のグラフト率で高分子電解質複合体グラフト不織
布を得た。Example 1 A non-woven fabric made of polypropylene fiber having a fiber diameter of 40 μm (CF-III manufactured by Kurashiki Fiber Processing Co., Ltd.) was irradiated with 200 kGy using an electron beam accelerator, and then sodium styrenesulfonate and trimethyl which had been previously deoxygenated were irradiated. In a 36% aqueous solution of a three-component mixture of vinylbenzylammonium salt and acrylic acid, reacted at 50 ° C. for 2 hours 30 minutes,
A polymer electrolyte composite grafted nonwoven fabric was obtained at a graft ratio of 61%.
【００１８】[0018]
【実施例２】ポリビニルアルコールをグラフト重合させ
たポリプロピレン製繊維よりなる不織布（倉敷繊維加工
社製：ＣＦ−ＩＩＩ）に電子線加速器を用いて、１００
ｋＧｙを照射した後、予め脱酸素したスチレンスルホン
酸ナトリウムとトリメチルビニルベンジルアンモニウム
の混合１０％水溶液中、７０℃で３時間反応させ、１３
３％のグラフト率で高分子電解質複合体グラフト不織布
を得た。Example 2 A nonwoven fabric (CF-III, manufactured by Kurashiki Fiber Processing Co., Ltd.) made of polypropylene fibers obtained by graft polymerization of polyvinyl alcohol was subjected to electron beam acceleration using an electron beam accelerator.
After irradiation with kGy, the mixture was reacted at 70 ° C. for 3 hours in a mixed 10% aqueous solution of sodium styrenesulfonate and trimethylvinylbenzylammonium which had been previously deoxygenated.
A polyelectrolyte composite graft nonwoven fabric was obtained at a graft ratio of 3%.
【００１９】[0019]
【実施例３】エチレンとビニルアルコールの共重合体よ
りなる膜厚１５μｍのフィルム（昭和電工社製）に電子
線加速器を用いて１００ｋＧｙを照射した後、予め脱酸
素したスチレンスルホン酸ナトリウムとトリメチルビニ
ルベンジルアンモニウム塩の混合１０％水溶液中、７０
℃で２時間３０分反応させ、６０％のグラフト率で高分
子電解質複合体グラフトフィルムを得た。Example 3 A 15 μm-thick film made of a copolymer of ethylene and vinyl alcohol (manufactured by Showa Denko KK) was irradiated with 100 kGy using an electron beam accelerator, and then sodium styrenesulfonate and trimethylvinyl which had been deoxygenated in advance were used. In a mixed 10% aqueous solution of benzyl ammonium salt, 70%
The reaction was carried out at a temperature of 2 ° C. for 2 hours and 30 minutes to obtain a polymer electrolyte composite graft film at a graft ratio of 60%.
【００２０】[0020]
【発明の効果】本発明により、形状自由で、物理的強度
に優れた高分子電解質複合体の製造が可能となった。According to the present invention, it has become possible to produce a polymer electrolyte composite having a free shape and excellent physical strength.
フロントページの続き (72)発明者 筒井 ▲つよし▼ 新潟県新津市滝谷本町１番26号 日揮化 学株式会社 新津事業所内 (56)参考文献 特開 昭58−10367（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 7/18 Continuation of the front page (72) Inventor Tsutsui ▲ Tsuyoshi ▼ 1-26 Takiya Honcho, Niitsu City, Niigata Prefecture Nikki Kagaku Co., Ltd. Niitsu Office (56) References JP-A-58-10367 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C08J 7/18
Claims (1)
くは不織布、又は膜状材料へ成型加工した高分子基材
に、カチオン基を持つモノマー及びアニオン基を持つモ
ノマーを放射線照射処理によりグラフト重合させること
からなる高分子電解質複合体の製造方法において、 カチオン基を持つモノマーが四級アンモニウム基を有す
るビニルベンジルトリメチルアンンモニウム塩であり、
アニオン基を持つモノマーがスチレンスルホン酸塩であ
ることを特徴とする、前記方法。1. A monomer having a cationic group and a monomer having an anionic group are irradiated to a single fiber, a woven or non-woven fabric which is an aggregate of single fibers, or a polymer base material formed into a film-like material by radiation irradiation treatment. A method for producing a polymer electrolyte composite comprising graft-polymerizing, wherein the monomer having a cationic group is a vinylbenzyltrimethylammonium salt having a quaternary ammonium group,
The above method, wherein the monomer having an anionic group is a styrene sulfonate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20804392A JP3218090B2 (en) | 1992-08-04 | 1992-08-04 | Manufacturing method of polymer electrolyte composite |
| US08/491,307 US5648400A (en) | 1992-08-04 | 1995-06-16 | Process for producing polymeric electrolyte complex and ion-exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20804392A JP3218090B2 (en) | 1992-08-04 | 1992-08-04 | Manufacturing method of polymer electrolyte composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0649252A JPH0649252A (en) | 1994-02-22 |
| JP3218090B2 true JP3218090B2 (en) | 2001-10-15 |
Family
ID=16549702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20804392A Expired - Fee Related JP3218090B2 (en) | 1992-08-04 | 1992-08-04 | Manufacturing method of polymer electrolyte composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3218090B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010074773A1 (en) * | 2008-12-23 | 2010-07-01 | 3M Innovative Properties Company | Functionalized nonwoven article |
| JP2019058843A (en) * | 2017-09-25 | 2019-04-18 | 株式会社Ihi | Multifunctional membrane and manufacturing method therefor |
-
1992
- 1992-08-04 JP JP20804392A patent/JP3218090B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0649252A (en) | 1994-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5648400A (en) | Process for producing polymeric electrolyte complex and ion-exchange resin | |
| Mizutani | Structure of ion exchange membranes | |
| CA1104008A (en) | Hydrophilic porous structures and process for production thereof | |
| US3375208A (en) | Method for preparing a microporous thermoplastic resin material | |
| US3546142A (en) | Polyelectrolyte structures | |
| Gupta et al. | Crosslinked ion exchange membranes by radiation grafting of styrene/divinylbenzene into FEP films | |
| CA2499515A1 (en) | Process for preparing graft copolymers useful in membranes | |
| JPH0724314A (en) | Chelate type ion adsorbing film and production thereof | |
| KR101188267B1 (en) | Anion exchange composite membrane with olefin-based additives and method for preparing the same | |
| Mizutani et al. | Studies on ion‐exchange membranes. XXXII. Heterogeneity in ion‐exchange membranes | |
| JP3245454B2 (en) | Production method of ion exchange resin | |
| JP3218090B2 (en) | Manufacturing method of polymer electrolyte composite | |
| US3271292A (en) | Ion exchange membranes and spacers and process of making them | |
| US3759738A (en) | Graft polymeric substrate | |
| US2884387A (en) | Porous membrane materials and process for producing the same | |
| US4608393A (en) | Process for producing an ion exchange membrane using irradiation by ionizing radiation followed by thermal polymerization | |
| US4083768A (en) | Preparation of high performance polyelectrolyte membrane | |
| WO2003018655A1 (en) | Process for preparing graft copolymer membranes | |
| US5543045A (en) | Charge mosaic membrane and production process thereof | |
| JP2504885B2 (en) | Ion exchanger manufacturing method | |
| KR101681637B1 (en) | Styrene-tert-butyl styrene based cation exchange composite membranes with nitrile rubber and method for preparing the same | |
| JP3555967B2 (en) | Method for producing elution-resistant anion-adsorbing membrane and membrane thereof | |
| ES366576A1 (en) | Cation exchange membranes and their preparation | |
| KR101190732B1 (en) | Cation exchange composite membranes with olefin-based additives and method for preparing the same | |
| Tsyurupa et al. | On factors determining the swelling ability of crosslinked polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070803 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080803 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080803 Year of fee payment: 7 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080803 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080803 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090803 Year of fee payment: 8 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090803 Year of fee payment: 8 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090803 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100803 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110803 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |