JPH01242145A - Oxygen adsorbent and sheet thereof - Google Patents
Oxygen adsorbent and sheet thereofInfo
- Publication number
- JPH01242145A JPH01242145A JP6740488A JP6740488A JPH01242145A JP H01242145 A JPH01242145 A JP H01242145A JP 6740488 A JP6740488 A JP 6740488A JP 6740488 A JP6740488 A JP 6740488A JP H01242145 A JPH01242145 A JP H01242145A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- sheet
- adsorbent
- reduced
- thermoplastic resin
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000001301 oxygen Substances 0.000 title claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 33
- 239000003463 adsorbent Substances 0.000 title claims abstract description 25
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 230000035699 permeability Effects 0.000 claims abstract description 3
- 229920002050 silicone resin Polymers 0.000 claims abstract description 3
- -1 polyethylene Polymers 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 14
- 229920000767 polyaniline Polymers 0.000 abstract description 14
- 239000000843 powder Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000002253 acid 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、吸着剤に係り、特に酸素吸着に好適な吸着剤
及びそのシートに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adsorbent, and particularly to an adsorbent suitable for oxygen adsorption and a sheet thereof.
可塑的な酸素吸着剤に関してはゼオライト鉱物など、微
細孔の発達した吸着剤が実用に供されている。例えば、
［ゼオライト−基礎と応用−（講談社出版）頁２３９か
ら頁２４０に記載。酸素のみの選択吸着を行なうために
は、吸着温度を下げる、加圧するなどの操作が必要とな
り、極めて装置が大がかりとなり、一般民生用には使用
できない。一方、非可塑的な酸素吸着としては、鉄粉等
の金属微粉末、ピロガロール等の酸素吸着剤が良く知ら
れ、実用に供されている。Regarding plastic oxygen adsorbents, adsorbents with developed micropores such as zeolite minerals are in practical use. for example,
[Described in Zeolite - Basics and Applications - (Kodansha Publishing) pages 239 to 240. In order to selectively adsorb only oxygen, operations such as lowering the adsorption temperature and applying pressure are required, which makes the device extremely large and cannot be used for general consumer use. On the other hand, as non-plastic oxygen adsorbers, fine metal powders such as iron powder and oxygen adsorbents such as pyrogallol are well known and are in practical use.
しかし、鉄粉等の金属粉を用いる場合には、重量効率が
悪いこと、吸着反応が１通常表面に限られること、成形
性が悪いことなどの欠点を有している。However, when metal powder such as iron powder is used, it has disadvantages such as poor weight efficiency, adsorption reaction being usually limited to one surface, and poor formability.
本発明は、軽量で成形性の自由な酸素選択吸着材を提供
することにある。An object of the present invention is to provide an oxygen selective adsorbent that is lightweight and has free formability.
この発明を概説すれば、酸化重合したアニリン重合体を
還元し、還元体のポリアニリンとし、この粉末と熱可塑
性樹脂を混練し、シート状としたものである。酸化重合
したポリアニリン粉末を、熱可塑性樹脂と混合し、シー
ト状とした後に、還元処理をすることも可能である。To summarize this invention, an oxidatively polymerized aniline polymer is reduced to obtain reduced polyaniline, and this powder is kneaded with a thermoplastic resin to form a sheet. It is also possible to mix the oxidatively polymerized polyaniline powder with a thermoplastic resin and form it into a sheet, followed by reduction treatment.
ポリアニリンは、電気化学的にも化学的にも合成が可能
であるが、製造工程の繁雑さ、及び合成されたポリアニ
リンのモルフオロジーから、酸素吸着剤としての性能は
、化学合成品の方がより高性能である。ポリアニリンは
、暗緑色の粉末として回収され、この高分子は、アニオ
ン（例えばＣＱ ０４−、 Ｂ Ｆ４−、 Ｓ
０４−−、 ＣＱ−、Ｂ ｒ−。Polyaniline can be synthesized both electrochemically and chemically, but due to the complexity of the manufacturing process and the morphology of the synthesized polyaniline, chemically synthesized products have better performance as oxygen adsorbents. High performance. Polyaniline was recovered as a dark green powder, and the polymer was composed of anions (e.g. CQ04-, BF4-, S
04--, CQ-, Br-.
ＣＯ２−一等）を含む酸化重合物であるため、酸素吸着
剤として還元処理の順序は、前述した如くシート形状と
した後でもよい。還元の方法としては、電気化学的な方
法と化学的な方法とがあるが、電気化学的な方法では、
得られた重合体の電気抵抗の問題から、完全な還元体を
得ることは難かしい。Since it is an oxidized polymer containing CO2-1, etc., the order of reduction treatment as an oxygen adsorbent may be after forming it into a sheet shape as described above. There are two methods of reduction: electrochemical and chemical methods.
Due to the electrical resistance of the obtained polymer, it is difficult to obtain a completely reduced product.
そのため、還元処理はヒドラジン等の還元剤を用いる化
学還元処理の方がより望ましい。例えば、ヒドラジンに
よる還元処理では、ヒドラジン水溶液中に所定の時間（
５時間以上）重合体を浸漬することによりなされる。Therefore, it is more desirable for the reduction treatment to be a chemical reduction treatment using a reducing agent such as hydrazine. For example, in reduction treatment with hydrazine, a predetermined period of time (
5 hours or more) by soaking the polymer.
混合する熱可塑性樹脂としては、ポリエチレン。The thermoplastic resin to be mixed is polyethylene.
ポリプロピレン、シリコン樹脂、ポリテトラフルオロエ
チレン、天然ゴム等の酸素透過性の高い樹脂が望ましい
。混合は粉末状態で行なうことも、加熱溶融下での混合
も可能である。添加する樹脂の量により、任意の形状に
することが可能であり、また塗布することもできる。Resins with high oxygen permeability such as polypropylene, silicone resin, polytetrafluoroethylene, and natural rubber are desirable. Mixing can be carried out in powder form or under heating and melting. Depending on the amount of resin added, it is possible to form it into any shape, and it can also be coated.
シート状としたものを酸素不透過性の膜（例えばアルミ
ニウム箔、ステンレス箔等）あるいは酸素難透過性の樹
脂フィルム（例えばポリ塩化ビニル、ポリ塩化ビニリデ
ン等）とラミネートし、袋状としたり、これらの金属板
、樹脂板の内張りとすることもよい。The sheet-like material is laminated with an oxygen-impermeable membrane (e.g., aluminum foil, stainless steel foil, etc.) or a poorly oxygen-permeable resin film (e.g., polyvinyl chloride, polyvinylidene chloride, etc.) and made into a bag-like form. It may also be lined with a metal plate or resin plate.
還元ポリアニリンの色調は淡黄色であり、混合する樹脂
との量比によっては、はぼ透明体となる。The color tone of reduced polyaniline is pale yellow, and depending on the amount ratio of the resin to be mixed, the reduced polyaniline becomes almost transparent.
酸素吸着が進行すると、ポリアニリンの色調は青色へと
移行する。これにより、吸着剤の酸素吸着状態が評価で
きる。As oxygen adsorption progresses, the color tone of polyaniline shifts to blue. Thereby, the oxygen adsorption state of the adsorbent can be evaluated.
以下１本発明による実施例を説明する。本発明は本実施
例のみに限定されるものではない。An embodiment according to the present invention will be described below. The present invention is not limited to this example.
第１実施例
アニリン（０，５ｍｏＱ／Ｑ）の塩酸水溶液中に４方硫
酸アンモニウム溶液を滴下し、アニリンを酸化重合析出
させた。重合反応温度は４０℃である。First Example A four-way ammonium sulfate solution was dropped into an aqueous hydrochloric acid solution of aniline (0.5 moQ/Q) to precipitate aniline by oxidative polymerization. The polymerization reaction temperature was 40°C.
濾別後、１ｍｏＱ／Ｑのアンモニア水にて中和処理し、
水洗後１２０℃にて乾燥した。この酸水状態のポリアニ
リン粉末に、１０ｗｔ％のポリエチレン粉末を乾式にて
混合し、８０℃の加熱ロールを用いてシート状に加工し
た。シートの厚みは０．５圃である。このシートをヒド
ラジン水溶液中に２４時間浸漬し還元処理を行なった。After filtering, neutralize with 1moQ/Q ammonia water,
After washing with water, it was dried at 120°C. This polyaniline powder in an acid water state was mixed with 10 wt % polyethylene powder in a dry method, and processed into a sheet using a heated roll at 80°C. The thickness of the sheet is 0.5 fields. This sheet was immersed in an aqueous hydrazine solution for 24 hours to perform a reduction treatment.
シートの色は淡黄色である。水洗・乾燥（不活性ガス中
）後。The color of the sheet is pale yellow. After washing with water and drying (in inert gas).
このシートｌＯａ＋ｆを酸素濃度Ｑ 、 １ ｖｏ１％
（残窒素ガス）中（容積５００ｍＱ）に放置した所、室
温下３日後に酸素濃度は１０ｐｐｎ＋まで低下した。This sheet lOa+f is oxygen concentration Q, 1 vo1%
When left in (residual nitrogen gas) (volume 500 mQ), the oxygen concentration decreased to 10 ppn+ after 3 days at room temperature.
第２実施例
第１実施例にて合成したポリアニリン粉末をアンモニア
水にて中和後、ヒドラジン水溶液にて還元処理し１２０
℃にて真空乾燥した。得られた粉末に、ポリプロピレン
を５０ｗｔ％添加し、５０μｍのシートに成形した後、
２軸延伸した。本シートを３枚重ね、差圧０．２ ｋｇ
／ｊにて、酸素２０ＰＰＩｍを含む窒素ガスを流した所
、得られたガス中の酸素濃度は１ ｐｐｍ＋以下であっ
た。Second Example The polyaniline powder synthesized in the first example was neutralized with ammonia water and then reduced with a hydrazine aqueous solution to 120%
Vacuum drying was performed at ℃. After adding 50 wt% of polypropylene to the obtained powder and molding it into a 50 μm sheet,
Biaxially stretched. 3 sheets stacked, differential pressure 0.2 kg
/j, when nitrogen gas containing 20 PPIm of oxygen was flowed, the oxygen concentration in the obtained gas was 1 ppm+ or less.
第３実施例
第１実施例と同様のシートを、ポリ塩化ビニリデンシー
トとラミネート処理し、ポリアニリンを内側にして袋状
物とし、真空封止した。２ケ月間ポリアニリンの色調は
変化しなかった。針にてピンホールをあけた所、ポリア
ニリンシートの色は徐々に青色に着色した。Third Example A sheet similar to that in the first example was laminated with a polyvinylidene chloride sheet to form a bag with polyaniline inside, and the bag was sealed in vacuum. The color tone of the polyaniline did not change for two months. When a pinhole was made with a needle, the polyaniline sheet gradually turned blue.
本発明によれば、吸着剤をシート状等任意の形状にする
ことができるので、容器に合わせた吸着材の加工が可能
であり、取扱いが容易である。また、酸素吸着により、
吸着剤シートの色調が変化するため、吸着量の推定、酸
素濃度の評価ができる。According to the present invention, since the adsorbent can be made into any shape such as a sheet, the adsorbent can be processed to match the container and is easy to handle. In addition, due to oxygen adsorption,
Since the color tone of the adsorbent sheet changes, it is possible to estimate the amount of adsorption and evaluate the oxygen concentration.
本発明によれば、アニリン重合物の還元体と熱可塑性樹
脂とを混合し成型することにより、使用目的に合わせた
任意の酸素吸着剤を提供できる効果がある。According to the present invention, by mixing and molding a reduced product of an aniline polymer and a thermoplastic resin, it is possible to provide any oxygen adsorbent suitable for the purpose of use.
Claims (1)
樹脂と、混合し成型した酸素吸着剤。 ２、前記アニリンの重合物が化学的酸化重合物である請
求項１に記載の酸素吸着剤。 ３、前記熱可塑性樹脂が、酸素透過性を有するポリエチ
レン、ポリプロピレン、シリコン樹脂、ポリテトラフル
オロエチレン、天然ゴムの内の一つである請求項１に記
載の酸素吸着剤。 ４、請求項１又は請求項３に記載の酸素吸着剤のシート
の片面を酸素不透過性膜と接合した酸素吸着剤シート。 ５、請求項１又は請求項３に記載の酸素吸着剤のシート
の片面を酸素難透過性の熱可塑性樹脂膜と接合した酸素
吸着剤シート。[Claims] 1. An oxygen adsorbent obtained by reducing a polymer of aniline to a reduced form, mixing it with a thermoplastic resin, and molding it. 2. The oxygen adsorbent according to claim 1, wherein the aniline polymer is a chemically oxidized polymer. 3. The oxygen adsorbent according to claim 1, wherein the thermoplastic resin is one of oxygen permeable polyethylene, polypropylene, silicone resin, polytetrafluoroethylene, and natural rubber. 4. An oxygen adsorbent sheet obtained by bonding one side of the oxygen adsorbent sheet according to claim 1 or claim 3 with an oxygen-impermeable membrane. 5. An oxygen adsorbent sheet in which one side of the oxygen adsorbent sheet according to claim 1 or claim 3 is joined to a thermoplastic resin film having low oxygen permeability.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6740488A JPH01242145A (en) | 1988-03-23 | 1988-03-23 | Oxygen adsorbent and sheet thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6740488A JPH01242145A (en) | 1988-03-23 | 1988-03-23 | Oxygen adsorbent and sheet thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01242145A true JPH01242145A (en) | 1989-09-27 |
Family
ID=13343969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6740488A Pending JPH01242145A (en) | 1988-03-23 | 1988-03-23 | Oxygen adsorbent and sheet thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01242145A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05115776A (en) * | 1991-04-02 | 1993-05-14 | W R Grace & Co | Mixture, product and method for scavenging oxygen |
-
1988
- 1988-03-23 JP JP6740488A patent/JPH01242145A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05115776A (en) * | 1991-04-02 | 1993-05-14 | W R Grace & Co | Mixture, product and method for scavenging oxygen |
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