JPS6140760B2 - - Google Patents
Info
- Publication number
- JPS6140760B2 JPS6140760B2 JP60091130A JP9113085A JPS6140760B2 JP S6140760 B2 JPS6140760 B2 JP S6140760B2 JP 60091130 A JP60091130 A JP 60091130A JP 9113085 A JP9113085 A JP 9113085A JP S6140760 B2 JPS6140760 B2 JP S6140760B2
- Authority
- JP
- Japan
- Prior art keywords
- quaternary ammonium
- polystyrene
- salt
- bromite
- based quaternary
- 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
Links
- 239000004793 Polystyrene Substances 0.000 claims description 28
- 229920002223 polystyrene Polymers 0.000 claims description 28
- DKSMCEUSSQTGBK-UHFFFAOYSA-M bromite Inorganic materials [O-]Br=O DKSMCEUSSQTGBK-UHFFFAOYSA-M 0.000 claims description 25
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- -1 hydroxide ions Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009990 desizing Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリスチレン系臭化四級アンモニウ
ム塩を液体媒体中で電解酸化することを特徴とす
るポリスチレン系亜臭素酸四級アンモニウム塩の
製造法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to the production of a polystyrene-based quaternary ammonium bromite salt, which is characterized by electrolytically oxidizing a polystyrene-based quaternary ammonium bromide salt in a liquid medium. Regarding the law.
亜臭素酸塩は、繊維の糊抜き剤として、不各種
有機化学反応の酸化剤として使用される貴重な化
学薬品である。 Bromite is a valuable chemical used as a desizing agent for textiles and as an oxidizing agent in a variety of organic chemical reactions.
従来の亜臭素酸化合物の製法としては、例えば
アルカル水溶液中に臭素と塩素を通じる方法（特
公昭39−25543号公報）、臭化水素酸塩を過酸化水
素と反応させる方法等がある。
Conventional methods for producing bromite compounds include, for example, a method in which bromine and chlorine are introduced into an aqueous alkali solution (Japanese Patent Publication No. 39-25543), a method in which a hydrobromide salt is reacted with hydrogen peroxide, and the like.
上記従来の製造法においては、前者は副反応が
生成し易く収率が低いこと、またその反応生成物
は塩化物、臭化物が混合した水溶液であるので、
通常はこの溶液そのものを糊抜き剤として使用す
る以外には、その用途が殆んどなく、また、後者
は高価な過酸化水素を使用する他、さらにこれを
製造する際に爆発の危険性がありいずれも好まし
い方法ではなかつた。
In the conventional production method described above, the former tends to produce side reactions and has a low yield, and the reaction product is an aqueous solution containing a mixture of chloride and bromide.
Normally, this solution itself has little use other than as a desizing agent, and the latter uses expensive hydrogen peroxide, and there is a risk of explosion when manufacturing it. None of these methods were preferred.
そのうえ、亜臭素酸はアルカリ塩であつても不
安定であるので、通常は濃厚なアルカリ水溶液と
して保存する必要があり、アルカリ水溶液として
種々の用途に供されている現状である。 Moreover, since bromous acid is unstable even in the form of an alkaline salt, it usually needs to be stored as a concentrated alkaline aqueous solution, and at present it is used for various purposes as an alkaline aqueous solution.
元来、亜臭素酸塩は有機化学反応における良好
な酸化剤としての適性を有するにもかかわらず、
上記の不安定性に基く制約があるため、その利用
が制限されているので、安定な亜臭素酸塩の開発
が望まれていた。 Despite the inherent suitability of bromite as a good oxidizing agent in organic chemical reactions,
Since the above-mentioned instability-based constraints limit its use, it has been desired to develop a stable bromite salt.
本発明者は安定な亜臭素酸塩の製造方法を鋭意
研究した結果ポリスチレン系臭化四級アンモニウ
ム塩を液体中で電解酸化することにより、ポリス
チレン系亜臭素酸四級アンモニウム塩が容易に得
られ、このポリスチレン系亜臭素酸四級アンモニ
ウム塩は空気中に長時間放置しても変質せず、極
めて安定であることを見い出し、本発明を完成す
るに到つた。即ち、本発明は
で表わされるポリスチレン系臭化四級アンモニウ
ム塩を液体中で電解酸化することを特徴とする
で表わされるポリスチレン系亜臭素酸四級アンモ
ニウム塩の製造法である。
As a result of intensive research into a method for producing stable bromite, the present inventor found that a polystyrene-based quaternary ammonium bromide salt can be easily obtained by electrolytically oxidizing a polystyrene-based quaternary ammonium bromide salt in a liquid. They discovered that this polystyrene-based quaternary ammonium bromite salt does not deteriorate even when left in the air for a long period of time and is extremely stable, leading to the completion of the present invention. That is, the present invention It is characterized by electrolytically oxidizing a polystyrene-based quaternary ammonium bromide salt represented by This is a method for producing a polystyrene-based quaternary ammonium bromite salt represented by:
本発明は、次式〔〕で示される。 The present invention is represented by the following formula [].
また、本発明においては、反応系中でポリスチ
レン系臭化四級アンモニウム塩が形成され、さら
に式（）の反応によりポリスチレン系亜臭素酸
四級アンモニウム塩に酸化される反応も含む。即
ち次式（）により、臭化水素酸又は、その塩が
反応系中において、ポリスチレン系四級アンモニ
ウム塩との交換反応により、ポリスチレン系臭化
四級アンモニウム塩が形成され、つづいて式
（）により酸化される反応である。式（）
Ｘは臭素以外の陰イオンを示し、Ｙは四級
アンモニウム以外の陽イオンを示す。 The present invention also includes a reaction in which a polystyrene-based quaternary ammonium bromide salt is formed in the reaction system, and is further oxidized to a polystyrene-based quaternary ammonium bromite salt by the reaction of formula (). That is, according to the following formula (), a polystyrene-based quaternary ammonium bromide salt is formed by an exchange reaction of hydrobromic acid or its salt with a polystyrene-based quaternary ammonium salt in the reaction system, and then the formula () This is a reaction in which oxidation is caused by formula() X represents an anion other than bromine, and Y represents a cation other than quaternary ammonium.
本発明でいうポリスチレン系四級アンモニウム
塩とは、スチレンを主成分とする重合体の主鎖あ
るいは側鎖に四級アンモニウム基が結合した重合
体を意味し、例えば、ポリスチレンのベンゼン環
にメチレン又はアルキレン基を介して四級アンモ
ニウム基が結合したもの、又、四級アンモニウム
基から成る単量体単位と他の単量体の共重合体あ
るいはその架橋された共重合体であつてもよく、
例えばスチレン−メタアクリル酸−ビニルピリジ
ン共重合体、スチレン−ジビニルベンゼン−ビニ
ルピリジン共重合体のピリジン基、が四級化され
たもの、又はベンゼン環がメチレン基を介して四
級化されたもの、スチレン−ジビニルベンゼンの
共重合体のベンゼン環にメチレン基を介して四級
アンモニウム基が結合したもの等をあげることが
できる。 The term "polystyrene-based quaternary ammonium salt" as used in the present invention refers to a polymer in which a quaternary ammonium group is bonded to the main chain or side chain of a polymer whose main component is styrene. For example, methylene or It may be one in which a quaternary ammonium group is bonded via an alkylene group, or a copolymer of a monomer unit consisting of a quaternary ammonium group and another monomer, or a crosslinked copolymer thereof.
For example, a styrene-methacrylic acid-vinylpyridine copolymer, a styrene-divinylbenzene-vinylpyridine copolymer whose pyridine group is quaternized, or a benzene ring quaternized via a methylene group. Examples include a styrene-divinylbenzene copolymer in which a quaternary ammonium group is bonded to the benzene ring via a methylene group.
通常、本発明の目的に使用する好適なものとし
ては、市販の強塩基性のアニオン交換樹脂が好適
である。 Generally, commercially available strongly basic anion exchange resins are suitable for use in the purpose of the present invention.
Ｘは、電解酸化条件でポリスチレン系亜臭素
酸四級アンモニウム塩の生成を阻害しないもので
あれば良く、特に限定しないが、水酸イオン、フ
ツ素、塩素等のハロゲンイオン、過塩素酸イオ
ン、亜硫酸イオン、亜硫酸水素イオン、硫酸イオ
ン、硫酸水素イオン等が挙げられ、Ｙとして
は、アルカリ金属又はアルカリ土類金属が好まし
い例として挙げられるが、これに限定されるもの
でない。 X may be any substance that does not inhibit the production of polystyrene-based quaternary ammonium bromite under electrolytic oxidation conditions, and is not particularly limited, but may include hydroxide ions, fluorine, halogen ions such as chlorine, perchlorate ions, Examples include sulfite ion, hydrogen sulfite ion, sulfate ion, hydrogen sulfate ion, etc., and Y is preferably an alkali metal or an alkaline earth metal, but is not limited thereto.
交換反応は、電解酸化の前に液体中で実施して
もよく、さらには電解槽中に一方の塩を過剰に存
在させ、他の塩を分添しながら電解酸化する方
法、両者の塩を同時に電解槽に分添する方法も採
用される。 The exchange reaction may be carried out in a liquid before electrolytic oxidation, and there is also a method in which one salt is present in excess in the electrolytic bath and electrolytically oxidized while adding the other salt, or a method in which both salts are mixed. At the same time, a method of adding portions to the electrolytic cell is also adopted.
本発明で使用する液体は水または水を含有する
有機溶媒であり、有機溶媒は水に可溶性、部分的
に可溶性、難溶性であつても良く、目的に応じ、
水及び有機溶媒の各々の単独又は混合物であつて
も良く、さらには、二相を形成する液体媒体の混
合物が好適に利用される場合もある。但し使用さ
れる有機溶媒は生成する亜臭素酸基によつて酸化
されるようなものの使用は避けるべきである。通
常は、水又は水と有機溶媒の均一又は不均一の混
合媒体が使用されるが、有機溶媒のみを媒体とし
て使用してもよく、臭素イオンが液体媒体中で遊
離されるような媒体を選択すればよい。 The liquid used in the present invention is water or an organic solvent containing water, and the organic solvent may be soluble, partially soluble, or poorly soluble in water, depending on the purpose,
Water and an organic solvent may be used alone or as a mixture, and a mixture of liquid media forming two phases may be preferably used. However, it is important to avoid using organic solvents that can be oxidized by the bromite groups produced. Typically, water or a homogeneous or heterogeneous mixed medium of water and an organic solvent is used, but it is also possible to use only an organic solvent as a medium, and the medium is selected such that bromide ions are liberated in the liquid medium. do it.
具体的な例としては、水の他に水を含有するア
ルコール類、エーテル類、アルコキシアルコール
類、ケトン類、アルキル炭化水素類、ハロゲン化
炭化水素類、ベンゼン系化合物及び非プロトン性
溶剤類が挙げられる。 Specific examples include water-containing alcohols, ethers, alkoxy alcohols, ketones, alkyl hydrocarbons, halogenated hydrocarbons, benzene compounds, and aprotic solvents. It will be done.
ポリスチレン系四級アンモニウム塩はスラリー
状で直接反応系に供給されるが、系のPHは９〜２
に保つことが好ましい。 The polystyrene quaternary ammonium salt is directly supplied to the reaction system in the form of a slurry, but the pH of the system is between 9 and 2.
It is preferable to keep it at
以上、ポリスチレン系臭化四級アンモニウム塩
基、及びポリスチレン系臭化四級アンモニウム塩
を反応系内で形成し得る臭化水素酸又はその塩と
ポリスチレン系四級アンモニウム塩の混合体につ
いて説明したが、これらの組成物は、電解槽の陽
極槽に供給される。一方、陰極液は、特に限定す
る必要はなく通常、電解反応において必要な電流
を流し得る各種溶液が用いられる。 The above describes the polystyrene-based quaternary ammonium bromide base and the mixture of hydrobromic acid or its salt and polystyrene-based quaternary ammonium salt that can form a polystyrene-based quaternary ammonium bromide salt in the reaction system. These compositions are fed to the anode cell of the electrolytic cell. On the other hand, the catholyte does not need to be particularly limited, and various solutions that can flow the necessary current in the electrolytic reaction are usually used.
電解酸化反応に使用される装置は、特別の配慮
を必要とせず通常の装置で良い。 The equipment used for the electrolytic oxidation reaction does not require any special consideration and may be a normal equipment.
陽極の材質は、白金、二酸化鉛、二酸化マンガ
ン、炭素系材料等を例として挙げることができ、
陰極の材質は、白金、鉄、鉛、銅等の金属材料又
は炭素系材料を例として挙げることができる。 Examples of the material of the anode include platinum, lead dioxide, manganese dioxide, carbon-based materials, etc.
Examples of the material of the cathode include metal materials such as platinum, iron, lead, and copper, or carbon-based materials.
陽極及び陰極の材質として上記に具体例を挙げ
たが、これに限定されるものでなく、又陽極及び
陰極の形状も使用する電解槽の形状によつて適当
に決めるべきであり、平板状、同筒板状、円柱
状、網状等のものが使用される。 Specific examples of the materials for the anode and cathode are given above, but the material is not limited to these, and the shape of the anode and cathode should also be determined appropriately depending on the shape of the electrolytic cell to be used. Cylindrical, plate-shaped, cylindrical, net-shaped, etc. are used.
陽極液と陰極液を隔離する隔膜は、素焼板の外
に各種の膜が使用できる。 As the diaphragm that separates the anolyte and catholyte, various types of membranes can be used in addition to the clay plate.
陽極液に供給されるポリスチレン系四級アンモ
ニウム塩の量は、陽極液中にイオン交換量として
0.01〜２モル／、好ましくは0.05〜0.5モル／
である。又特別の装置を用いる場合は、この範囲
外であつてもよい。 The amount of polystyrene quaternary ammonium salt supplied to the anolyte is determined by the amount of ion exchange in the anolyte.
0.01-2 mol/, preferably 0.05-0.5 mol/
It is. In addition, when using special equipment, it may be outside this range.
通電は定電流及び定電圧のいづれの方法に従つ
ても良い。電流密度は陽極液の電解質濃度、その
他によつて最適値を決定すべきであるが、通常
1.5A/cm2以下、好ましくは0.005〜0.5A/cm2の範囲
である。 The current may be supplied using either a constant current method or a constant voltage method. The optimum current density should be determined depending on the electrolyte concentration of the anolyte and other factors, but usually
It is 1.5 A/cm 2 or less, preferably in the range of 0.005 to 0.5 A/cm 2 .
電解液の温度は０℃から80℃の範囲が適当であ
り、低温側では反応速度の低下、高温側ではポリ
スチレン系亜臭素酸四級アンモニウム塩の収率の
低下が認められ、反応温度は上記の範囲で調節す
ることが望ましい。 The appropriate temperature for the electrolyte solution is between 0°C and 80°C.At low temperatures, the reaction rate decreases, and at high temperatures, the yield of polystyrene-based quaternary ammonium bromite salt decreases. It is desirable to adjust within the range of .
以下、実施例にて本発明をさらに具体的に説明
するが、本発明はこれに限定されるものでない。
EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例
電解槽は500mlのガラス製円筒容器を使用し、
この中に円筒状素焼隔膜（45φ×150）を入れ、
この内側を陽極室とし、陽極室に網状円筒形電極
（３φ×５）の陽極を設置し、外側の陰極室に
は、陰極として鉛板（80cm2）を設置した。Example: The electrolytic cell uses a 500ml glass cylindrical container.
Insert a cylindrical unglazed diaphragm (45φ x 150) into this,
The inside of this chamber was used as an anode chamber, and a reticular cylindrical anode (3φ×5) was installed in the anode chamber, and a lead plate (80 cm 2 ) was installed as a cathode in the outer cathode chamber.
陽極室に市販のポリスチレン系４級アンモニウ
ム塩のOH型を４ｇ（NAClにより、イオン交換
容量を測定したところ20ミリモルである）及び２
規定の臭化カリウム水溶液100mlを供給し、陰極
室には２規定の臭化カリウム水溶液100mlを供給
した後、陽極室をマグネチツクスタラーで撹拌し
ながら電流密度0.5A/cm2で通電し、電解液の温度
を10℃に保つた。樹脂に対して4F／モルの通電
量で電解を行つた後、反応液から橙色に変色した
樹脂をデカンテーシヨンで分離し、水洗、乾燥し
た。 In the anode chamber, 4 g of the OH form of a commercially available polystyrene quaternary ammonium salt (the ion exchange capacity was measured with NACl was 20 mmol) and 2
After supplying 100 ml of a specified potassium bromide aqueous solution and supplying 100 ml of a 2N potassium bromide aqueous solution to the cathode chamber, electricity was applied at a current density of 0.5 A/cm 2 while stirring the anode chamber with a magnetic stirrer. The temperature of the electrolyte was kept at 10°C. After electrolyzing the resin at a current flow rate of 4 F/mol, the orange-colored resin was separated from the reaction solution by decantation, washed with water, and dried.
この乾燥品につき、赤外分光光度計で分析した
ところBrO− ２の吸収（760cm-1）が確認された。ま
た、この樹脂を１規定のカ性ソーダ100mlに浸漬
し、亜臭素酸基をナトリウム塩として、溶液中に
溶解させた後、ヨウ素適定により亜臭素酸基量を
定量した結果亜臭素酸塩が19.6ミリモル（収率
98.0％）生成していた。 When this dried product was analyzed using an infrared spectrophotometer, absorption of BrO - 2 (760 cm -1 ) was confirmed. In addition, this resin was immersed in 100 ml of 1N caustic soda, and the bromite group was dissolved in the solution as a sodium salt.The amount of bromite group was determined by iodine titration. is 19.6 mmol (yield
98.0%) was generated.
本発明の作用効果としては、従来臭化水素酸塩
を電解すると臭素酸が得られることは知られてい
たが、この中間段階にあるポリスチレン系亜臭素
酸塩が電解により合成されることは全く知られて
いなかつたもので、本発明において、ポリスチレ
ン系四級アンモニウム塩を電解系に共存させるこ
とにより、初めて亜臭素酸塩をポリスチレン系四
級アンモニウム塩に結合することに成功したこと
である。
As an effect of the present invention, it has been known that bromic acid can be obtained by electrolyzing hydrobromide, but it has never been possible to synthesize polystyrene-based bromite, which is at this intermediate stage, by electrolysis. What was previously unknown is that in the present invention, for the first time, by coexisting a polystyrene-based quaternary ammonium salt in the electrolytic system, it was possible to successfully bind bromite to a polystyrene-based quaternary ammonium salt.
また、この本発明の方法により得られるポリス
チレン系亜臭素酸四級アンモニウム基の亜臭素酸
基は空気中に放置しても極めて安定であり、各
種、有機化学反応の酸化等に利用した後、ポリス
チレン系四級アンモニウム基は任意の方法で回収
し、再度、ポリスチレン系亜臭素酸四級アンモニ
ウム塩の製造に使用され、工業的にも有利な方法
である。 Furthermore, the bromite group of the polystyrene-based quaternary ammonium bromite group obtained by the method of the present invention is extremely stable even when left in the air, and after being used in various organic chemical reactions such as oxidation, The polystyrene-based quaternary ammonium group is recovered by any method and used again in the production of polystyrene-based bromite quaternary ammonium salt, which is an industrially advantageous method.
Claims (1)
ム塩を液体媒体中で電解酸化することを特徴とす
る で表わされるポリスチレン系亜臭素酸四級アンモ
ニウム塩の製造法。[Claims] 1 It is characterized by electrolytically oxidizing polystyrene-based quaternary ammonium bromide salt represented by in a liquid medium. A method for producing a polystyrene-based quaternary ammonium bromite salt represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60091130A JPS60258488A (en) | 1985-04-30 | 1985-04-30 | Manufacture of polystyrene bromous quaternary ammonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60091130A JPS60258488A (en) | 1985-04-30 | 1985-04-30 | Manufacture of polystyrene bromous quaternary ammonium salt |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54150359A Division JPS6040513B2 (en) | 1979-11-20 | 1979-11-20 | Production method of quaternary ammonium bromite salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60258488A JPS60258488A (en) | 1985-12-20 |
| JPS6140760B2 true JPS6140760B2 (en) | 1986-09-10 |
Family
ID=14017952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60091130A Granted JPS60258488A (en) | 1985-04-30 | 1985-04-30 | Manufacture of polystyrene bromous quaternary ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60258488A (en) |
-
1985
- 1985-04-30 JP JP60091130A patent/JPS60258488A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60258488A (en) | 1985-12-20 |
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