JPS6310628A - Production of polyaniline - Google Patents
Production of polyanilineInfo
- Publication number
- JPS6310628A JPS6310628A JP14883786A JP14883786A JPS6310628A JP S6310628 A JPS6310628 A JP S6310628A JP 14883786 A JP14883786 A JP 14883786A JP 14883786 A JP14883786 A JP 14883786A JP S6310628 A JPS6310628 A JP S6310628A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- electrolytic polymerization
- temperature
- polyaniline
- aniline
- 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
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 47
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical compound F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 101150073554 fliM gene Proteins 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
産ＪｕΔ上」１年１ｍ
本発明は、アニリンを電解重合してポリアニリンを製造
する際に発生す゛る副生成物、特に有害物質とされてい
るベンジジンの発生量の少ないポリアニリンの製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention aims to produce polyaniline with a small amount of by-products generated when producing polyaniline by electrolytically polymerizing aniline, especially benzidine, which is considered to be a harmful substance. Relating to a manufacturing method.
亘米坐肢翌 近年、ポリアニリンは、新しい電子材料として。Watarubei sitting limb next day In recent years, polyaniline has been used as a new electronic material.
電池、光電池、エレクトロクロミンクディスプレー、各
種修飾電極等の応用分野で注目されており、導電性、ｆ
ｌ気化学活性等の電子物性面での研究開発が盛んである
と共に、これらの電子物性を付与するポリアニリンの製
造方法の検討も盛んに行われている。その結果、アルカ
リ性溶液中で合成されたポリアニリンは電気化学的に不
活性で、電気化学的に活性なポリアニリンは硫酸等の酸
性水溶液中でアニリンを酸化重合することによって得ら
れること、この場合この酸化重合法の中でもエネルギー
密度（放電電流及び放電電圧）、各種電極材料としての
生産性等の点で、過硫酸塩の如き化学的酸イ’ｂ剤を用
いる化学的酸化法に比し、電解酸化（電解重合）法の方
が優れていることが見出されている。It is attracting attention in application fields such as batteries, photovoltaic cells, electrochromic displays, and various modified electrodes.
In addition to active research and development in terms of electronic properties such as chemical activity, studies are also being actively conducted on methods for producing polyaniline that imparts these electronic properties. As a result, polyaniline synthesized in an alkaline solution is electrochemically inactive, and electrochemically active polyaniline can be obtained by oxidative polymerization of aniline in an acidic aqueous solution such as sulfuric acid. Among polymerization methods, electrolytic oxidation is superior to chemical oxidation methods that use chemical acid bactericidal agents such as persulfates in terms of energy density (discharge current and discharge voltage) and productivity as various electrode materials. (electrolytic polymerization) method has been found to be superior.
■が じようとする間貞
しかしながら、本発明者らの検討によると電解重合法に
よりポリアニリンを製造した場合、重合液中にＩ ＰＰ
１１以下程以下値かな濃度ではあるが、ベンゾキノン、
Ｎ−フェニル−ｐ−フェニレンジアミン、ベンジジン等
が検出され、ｆｌｉＭ重合過程でこれら化合物が副生成
物として生成することが知見された。これら副生成物は
、ポリアニリンを電子材料に応用する場合、特性上好ま
しいものではなく、ポリアニリン製造段階で生成を抑止
し、あるいはポリアニリン製造後に除去することが良い
と考えられるものである。また、これら副生成物の中で
もベンジジンは人体に有害な物質であることが認められ
ており、人体に対する安全性の面からも極力その発生を
抑止することが必要とされる。However, according to the studies of the present inventors, when polyaniline is produced by electrolytic polymerization, IPP is present in the polymerization solution.
Although the concentration is probably below 11, benzoquinone,
N-phenyl-p-phenylenediamine, benzidine, etc. were detected, and it was found that these compounds were produced as by-products during the fliM polymerization process. These by-products are not desirable in terms of properties when polyaniline is applied to electronic materials, and it is thought that it is better to suppress their formation during the polyaniline production stage or to remove them after polyaniline production. Furthermore, among these by-products, benzidine is recognized as a substance harmful to the human body, and from the viewpoint of safety to the human body, it is necessary to suppress its generation as much as possible.
本発明は上記事情に鑑みなされたもので、電解重合法に
よりポリアニリンを製造する際、ＩＩ造過程で発生する
副生成物、とりわけベンジジンの発生が抑止されたポリ
アニリンを提供することを目的とする。The present invention was made in view of the above circumstances, and an object of the present invention is to provide polyaniline in which the generation of by-products, particularly benzidine, generated in the II production process when polyaniline is produced by electrolytic polymerization is suppressed.
ｒ１′占を するための び
本発明者らは、上記目的を達成するため電解重合法によ
りボリアごリンを製造する方法につき鋭意検討を行った
結果、アニリンを含む電解重合液の温度を１５℃以下に
制御して電解重合すると、重合後の電解重合液中に含ま
れるベンジジンの濃度が温度制御を行わずに高温状態で
電解重合した場合の半分以下となって、副生成物のベン
ジジンの発生量を大幅に低減できることを知見し、本発
明を完成するに至ったものである。To achieve the above objective, the present inventors conducted intensive studies on a method for producing boria phosphorus by electrolytic polymerization, and found that the temperature of the electrolytic polymer solution containing aniline was set at 15°C. When electropolymerization is performed under the following control, the concentration of benzidine contained in the electropolymerization solution after polymerization is less than half of that when electropolymerization is performed at high temperature without temperature control, and the by-product benzidine is generated. It was discovered that the amount could be significantly reduced, and the present invention was completed.
即ち１本発明はアニリンを電解重合してポリアニリンを
製造するに際し、アニリンを含む電解重合液の温度を１
５℃以下に制御して電解重合するポリアニリンの製造方
法を提供するものである。That is, 1. When producing polyaniline by electrolytically polymerizing aniline, the present invention lowers the temperature of the electrolytic polymerization solution containing aniline to 1
The present invention provides a method for producing polyaniline by electrolytically polymerizing the temperature at 5° C. or lower.
以下、本発明を更に詳しく説明する。The present invention will be explained in more detail below.
本発明のポリアニリンの製造方法は上述したようにアニ
リンを含む電解重合液の温度を１５℃以下に制御して電
解重合を行い、ポリアニリンを製造するものである。As described above, the method for producing polyaniline of the present invention involves controlling the temperature of an electrolytic polymerization solution containing aniline to 15° C. or less to carry out electrolytic polymerization to produce polyaniline.
これに対し、アニリンを含む電解重合液の温度が１５℃
を越える場合には、電解重合後において電解重合液中の
ベンジジンの濃度が大幅に増太し、電解重合液の廃液処
理等の取扱いに安全衛生上の注意が必要となるため、本
発明の目的に対し不適である。In contrast, the temperature of the electrolytic polymerization solution containing aniline was 15°C.
If the concentration exceeds the above, the concentration of benzidine in the electrolytic polymerization solution will increase significantly after electrolytic polymerization, and safety and hygiene precautions will be required when handling waste liquid of the electrolytic polymerization solution. unsuitable for
なお、温度の下限は電解重合液の凝固点である。Note that the lower limit of the temperature is the freezing point of the electrolytic polymerization liquid.
この場合、電解重合液の凝固点は主として電解重合液の
組成により異なり、−概に限定することはできない。例
えば、アニリン濃度１ｍｏΩ／Ω、酸としてホウフッ酸
を用いた酸濃度２ａ＋ｏＱ／Ｑの電解重合液の凝固点は
一１０℃程度である。In this case, the freezing point of the electrolytic polymerization solution varies mainly depending on the composition of the electrolytic polymerization solution, and cannot be generally limited. For example, the freezing point of an electrolytic polymerization solution with an aniline concentration of 1 moΩ/Ω and an acid concentration of 2a+oQ/Q using borofluoric acid as the acid is about -10°C.
ここで、アニリンの電解重合は、電子材料として好適な
ポリアニリンを製造する場合には、酸性の電解重合液を
用いて電解重合を行うことが好ましい。Here, in the electrolytic polymerization of aniline, when producing polyaniline suitable as an electronic material, it is preferable to perform the electrolytic polymerization using an acidic electrolytic polymerization solution.
この場合、電解重合液の組成に限定はなく、また電解条
件も電解重合液の温度以外には特に制限されず、通常の
組成、条件を採用することができ、製造すべきポリアニ
リンの膜厚や物性等を適宜選定することができるが、例
えば電解重合液としてはアニリン濃度０．０１〜５ｍｏ
Ｑ／Ｑ、とりわけ０ 、５〜３ｍｏ１２ ／ Ｑ及び酸
濃度０．０２〜１０ｍｏＱ／ｍ、とりわけ１〜６Ｉｌｏ
Ｑ／Ｑを含有し、酸としてフッ化水素酸、塩酸、硫酸、
硝酸、過塩素酸、ホウフッ化水素酸、酢酸等、中でも塩
酸、過塩素酸、ホウフッ化水素酸を使用したものが電子
材料として好適なポリアニリンを製造するのに好ましく
使用される。なお、この場合の陽極電流密度は５０ ｍ
Ａ ／ Ｃ！Ｊ程度以下、特に３０ｍＡ／ｃｄ程度以
下であり、またその下限としては０．１ｍＡ／ａｉ、特
に１ ｍ Ａ ／ ｄの条件が好適に採用される。In this case, there is no limit to the composition of the electrolytic polymerization solution, and the electrolytic conditions are not particularly limited other than the temperature of the electrolytic polymerization solution, and normal compositions and conditions can be adopted, and the thickness and thickness of the polyaniline to be produced can be adjusted. Physical properties etc. can be selected as appropriate, but for example, as an electrolytic polymerization solution, an aniline concentration of 0.01 to 5 mo
Q/Q, especially 0, 5-3 mo12/Q and acid concentration 0.02-10 moQ/m, especially 1-6 Ilo
Contains Q/Q, and the acids include hydrofluoric acid, hydrochloric acid, sulfuric acid,
Nitric acid, perchloric acid, hydrofluoroboric acid, acetic acid, etc., among others, those using hydrochloric acid, perchloric acid, and hydrofluoroboric acid are preferably used for producing polyaniline suitable as an electronic material. Note that the anode current density in this case is 50 m
A/C! J or less, especially about 30 mA/cd or less, and the lower limit thereof is preferably 0.1 mA/ai, especially 1 mA/d.
なお、電解重合液を上記所定の温度に制御する方法につ
いては特に制限されるものではないが、冷却媒体として
氷水や氷と食塩との寒剤を収容したバスを使用し、電解
重合液を収容する電解槽をこの冷却媒体を温度制御しな
がら冷却する方法、電解重合液を温度制御された冷却媒
体を通して循環するなどの方法が簡便な方法として採用
し得る。The method for controlling the electrolytic polymerization solution to the above-mentioned predetermined temperature is not particularly limited, but a bath containing ice water or a cold agent of ice and salt as a cooling medium may be used to contain the electrolytic polymerization solution. A method of cooling the electrolytic cell while controlling the temperature of the cooling medium, a method of circulating the electrolytic polymerization liquid through a temperature-controlled cooling medium, etc. can be adopted as a simple method.
ｌ匪匹例米
以上説明したように１本発明のポリアニリンの製造方法
は、アニリンを電解重合してポリアニリンを製造するに
際し、アニリンを含む電解重合液の温度を１５℃以下に
制御して電解重合するものであり、これにより電解重合
時に発生する人体に有害なベンジジンの発生量を大幅に
低減することができるものである。As explained above, in the method for producing polyaniline of the present invention, when producing polyaniline by electrolytically polymerizing aniline, the temperature of the electrolytic polymerization solution containing aniline is controlled to 15°C or less, and the electrolytic polymerization is carried out. This makes it possible to significantly reduce the amount of benzidine, which is harmful to the human body, generated during electrolytic polymerization.
以下、実施例と比較例を示し１本発明を具体的に説明す
るが、本発明は下記の実施例に制限されるものではない
。EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.
電解重合液としてアニリン２．７ｃｃ、４２ｗｔ％ホウ
フッ酸９．０ｃｃ、イオン交換水１８．３ｃｃからなる
ものを使用し、この電解重合液を見かけ面積４ｃｄ、直
径５０μｍ、９０メツシユの５ＵＳ３１６製金網からな
る動作電極及び対極を具備した電解槽に収容した。この
電解槽を氷水に浸して冷し、電解重合液の温度を略０℃
に保ちながら４０ｍＡの定電流で２．６時間通電して電
解重合を行った。An electrolytic polymerization solution consisting of 2.7 cc of aniline, 9.0 cc of 42 wt% borofluoric acid, and 18.3 cc of ion-exchanged water was used. It was placed in an electrolytic cell equipped with a working electrode and a counter electrode. This electrolytic cell is immersed in ice water to cool it down, and the temperature of the electrolytic polymerization solution is approximately 0°C.
Electrolytic polymerization was carried out by applying current at a constant current of 40 mA for 2.6 hours while maintaining the temperature.
次いで、上記電解重合後の電解重合液を分析したところ
、２０ｐｐｂ濃度のベンジジンが検出された。Next, when the electrolytic polymerization solution after the electrolytic polymerization was analyzed, benzidine was detected at a concentration of 20 ppb.
電解重合液を冷却せず、電解重合液の温度を室温（はぼ
２３℃）とした以外は実施例と同様にして電解重合を行
い、電解重合後の電解重合液を分析したところ、５０ｐ
Ｐｂ濃度のベンジジンが検出された。Electropolymerization was carried out in the same manner as in the example except that the electrolytic polymerization solution was not cooled and the temperature of the electrolytic polymerization solution was kept at room temperature (approximately 23°C). When the electrolytic polymerization solution after electrolytic polymerization was analyzed, it was found that 50p
Pb concentrations of benzidine were detected.
従って、実施例のベンジジンの量は比較例のそれの半分
以下であり、本発明の効果が確認された。Therefore, the amount of benzidine in the example was less than half of that in the comparative example, confirming the effect of the present invention.
Claims (1)
際し、アニリンを含む電解重合液の温度を１５℃以下に
制御して電解重合することを特徴とするポリアニリンの
製造方法。1. A method for producing polyaniline, which is characterized in that when producing polyaniline by electrolytically polymerizing aniline, the temperature of an electrolytic polymerization solution containing aniline is controlled at 15° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14883786A JPS6310628A (en) | 1986-06-24 | 1986-06-24 | Production of polyaniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14883786A JPS6310628A (en) | 1986-06-24 | 1986-06-24 | Production of polyaniline |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6310628A true JPS6310628A (en) | 1988-01-18 |
Family
ID=15461840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14883786A Pending JPS6310628A (en) | 1986-06-24 | 1986-06-24 | Production of polyaniline |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6310628A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04284757A (en) * | 1990-10-18 | 1992-10-09 | Delco Electron Corp | Corrugated shaping circuit |
-
1986
- 1986-06-24 JP JP14883786A patent/JPS6310628A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04284757A (en) * | 1990-10-18 | 1992-10-09 | Delco Electron Corp | Corrugated shaping circuit |
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