JPH0830107B2 - Electropolymerization of organic polymers - Google Patents
Electropolymerization of organic polymersInfo
- Publication number
- JPH0830107B2 JPH0830107B2 JP61023220A JP2322086A JPH0830107B2 JP H0830107 B2 JPH0830107 B2 JP H0830107B2 JP 61023220 A JP61023220 A JP 61023220A JP 2322086 A JP2322086 A JP 2322086A JP H0830107 B2 JPH0830107 B2 JP H0830107B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- electrode
- organic
- electrolytic
- electrolytic solution
- 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 - Lifetime
Links
- 229920000620 organic polymer Polymers 0.000 title claims description 23
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 description 33
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- -1 demethylformamide Chemical compound 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は有機高分子の電解重合法に関するものであ
る。特に、微粉末を含有した有機高分子の作成法に関す
るものである。TECHNICAL FIELD The present invention relates to an electrolytic polymerization method for organic polymers. In particular, it relates to a method for producing an organic polymer containing fine powder.
従来の技術 有機高分子、特に伝導性有機高分子の電解重合法は、
合成のコントロールが容易であること、特に導電性有機
高分子では、その物性において、電子伝導性をもつこ
と、半導体的特性を示すことから、活発に進められてい
る。例えば、有機高分子として、ポリピロールを例にと
ると、その電解重合は次の如く行なわれる。即ち、電解
液として、有機溶媒（例えば、アセトニトリル，デメチ
ルホルムアミド，プロピレンカーボネート等）に、ホウ
フッ化リチウム（LiBF4），過塩素酸リチウム（LiCl
O4）等の電解質を溶解した溶液中に重合したいモノマー
（この場合、ピロール）を溶解させた電解液を用い、該
電解液中に試料電極と対向電極、更に必要に応じて、試
料電極に印加する電位を規制するための参照電極を挿入
し、試料電極に正電圧を印加しながら、ピロールを電解
酸化することにより、ピロールポリマーを試料電極に重
合析出させている。このようにして得られた有機高分子
は、高分子内への陰イオンの出入りにより電子伝導性が
変化する性質と半導体特性を有する。これらの特性を使
用して、電池FETトランジスター，電磁波シールド材へ
の応用が検討されている。しかし、電池とした場合、そ
のエネルギー密度が比較的小さい事、FETトランジスタ
とした場合、従来のFETと比較して特徴が少ないなど、
その応用展開を活発に進めるための魅力に欠けていた。Conventional technology Electropolymerization of organic polymers, especially conductive organic polymers,
It is being actively promoted because it is easy to control the synthesis, and particularly in the case of a conductive organic polymer, its physical properties have electronic conductivity and semiconductor characteristics. For example, taking polypyrrole as the organic polymer, the electrolytic polymerization is carried out as follows. That is, as an electrolytic solution, an organic solvent (eg, acetonitrile, demethylformamide, propylene carbonate, etc.), lithium borofluoride (LiBF 4 ), lithium perchlorate (LiCl 4 ) is used.
O 4 ), etc., is used in an electrolyte solution in which a monomer (in this case, pyrrole) to be polymerized is dissolved in a solution in which a sample electrode and a counter electrode, and if necessary, a sample electrode A reference electrode for regulating the potential to be applied is inserted, and a pyrrole polymer is polymerized and deposited on the sample electrode by electrolytically oxidizing pyrrole while applying a positive voltage to the sample electrode. The organic polymer thus obtained has the property that the electronic conductivity is changed by the entry and exit of anions into the polymer and the semiconductor property. Utilizing these characteristics, application to battery FET transistors and electromagnetic wave shielding materials is being studied. However, when used as a battery, its energy density is relatively small, and when used as a FET transistor, it has fewer features than conventional FETs.
It lacked the appeal to actively promote its application development.
発明が解決しょうとする問題点 従来、前記機能以外に各種機能を保持した有機高分子
を作成する方法がなかった。本発明はそのような方法を
提供し、新しい機能を有した有機高分子を作成すること
にある。Problems to be Solved by the Invention Conventionally, there has been no method for producing an organic polymer having various functions other than the above-mentioned functions. The present invention provides such a method, and makes an organic polymer having a new function.
問題点を解決するための手段 各種機能を有した微粉末粒子を電解液中に含有させ、
有機モノマーを電解酸化重合させることにより、微粉末
粒子を有機高分子内に含有させる。Means for solving the problem Fine powder particles having various functions are contained in the electrolytic solution,
Fine powder particles are contained in the organic polymer by electrolytically oxidatively polymerizing the organic monomer.
作用 粒子を導体内に共折させることは、電気鍍金技術分野
において広く使われている。即ち、電気メッキ浴中に粒
子を分散させ、浴中の金属イオンを還元することによ
り、析出金属内に粒子を共折するものである。即ち、浴
中でに帯電している粒子が、金属イオンを還元する際
負極に引き寄せられ、金属と共に析出するとされてい
る。本発明は、前記現象が反応の全く異なる系である電
解酸化重合に適用出来ることを見出したものである。そ
の原因は明確でないが、単に機械的に粒子が電極表面に
接触すると同時に析出する有機高分子にトラップされる
ものとする。Co-folding working particles into conductors is widely used in the electroplating art. That is, the particles are dispersed in the electroplating bath and the metal ions in the bath are reduced to co-fold the particles in the deposited metal. That is, it is said that the particles charged in the bath are attracted to the negative electrode when the metal ions are reduced and deposited together with the metal. The present invention has found that the above phenomenon can be applied to electrolytic oxidative polymerization, which is a system having completely different reactions. The reason for this is not clear, but it is merely assumed that the particles are mechanically trapped in the organic polymer that is deposited at the same time when the particles come into contact with the electrode surface.
実施例 以下、実施例をもとに本発明を説明する。EXAMPLES Hereinafter, the present invention will be described based on examples.
実施例１ 第１図は本発明による電解重合装置に示したものであ
る。図中１はアノード室，カソード室を分離するガラス
よりなるセパレーター２を中間に介在させたガラス製の
電解槽である。３は有機高分子を得るため試料電極であ
り、４は試料電極３に印加する電位を規制するために使
用した参照電極で、こゝでは銀を用いた。５は白金電極
よりなる対向電極、６は電解液で、１％ピロールを含む
1M−LiBF4／アセトニトリルを用いた。７は微粉末粒子
で、こゝでは直径50μ以下の酸化タングステン（WO3）
粉末を用いた。８は電解液を拡はんするための拡はん棒
で9,10は各々拡はん棒へ支へるための軸受と回転を伝へ
るためのプーリである。該電解液を拡はんしながら、ポ
テシオスタツト11とファンクションゼネレーター12を用
い電解電位を規制しながら電解した。電解条件は20℃，
＋0.7V（VvsAg）で１時間、電解した。Example 1 FIG. 1 shows an electrolytic polymerization apparatus according to the present invention. In the figure, 1 is a glass electrolytic cell with a separator 2 made of glass for separating the anode chamber and the cathode chamber interposed in between. 3 is a sample electrode for obtaining an organic polymer, 4 is a reference electrode used for regulating the potential applied to the sample electrode 3, and silver is used here. 5 is a counter electrode made of a platinum electrode, 6 is an electrolytic solution, and contains 1% pyrrole
Using 1M-LiBF 4 / acetonitrile. 7 is a fine powder particle, and here, tungsten oxide (WO 3 ) with a diameter of 50 μm or less is used.
Powder was used. Reference numeral 8 is a spreading rod for spreading the electrolytic solution, and 9 and 10 are bearings for supporting the spreading rod and pulleys for transmitting rotation. Electrolysis was performed while the electrolytic solution was being spread and the electrolytic potential was regulated using a potentiostat 11 and a function generator 12. Electrolysis conditions are 20 ℃,
Electrolysis was performed at +0.7 V (VvsAg) for 1 hour.
実施例２ 電解液中に含有させる微粉末粒子として、直径50μ以
下の酸化タングステン（WO2）を用いた以外、実施例１
と全く同様にして、有機高分子を電解重合した。Example 2 Example 1 was repeated except that tungsten oxide (WO 2 ) having a diameter of 50 μm or less was used as the fine powder particles contained in the electrolytic solution.
The organic polymer was electrolytically polymerized in the same manner as in.
実施例３ 電解液中に含有させる粒子として、直径30μ以下の金
属タングステン粒子（Ｗ）を用いた以外は実施例１と全
く同様にして、有機高分子を電解重合した。Example 3 An organic polymer was electrolytically polymerized in exactly the same manner as in Example 1 except that metal tungsten particles (W) having a diameter of 30 μm or less were used as particles to be contained in the electrolytic solution.
以上、実施例１〜３によって出た有機高分子は直視的
にも、各粒子が入っていることを確認することが出来る
が、各々の膜に含まれる粒子をＸ線光電子分光装置によ
り確認した結果、各々の粒子について第２図の如きチャ
ートを得、有機高分子内に粒子の存在を確認した。As described above, the organic polymers produced in Examples 1 to 3 can be confirmed by direct observation that each particle is contained, but the particles contained in each film were confirmed by an X-ray photoelectron spectrometer. As a result, a chart as shown in FIG. 2 was obtained for each particle, and the existence of particles in the organic polymer was confirmed.
実施例４ 電解液中に含有させる粒子として、直径30μ以下の酸
化モリブデンを用い、実施例１の装置を用い電解重合し
た。この際、電解重合の為に電極に印加した電圧は、＋
0.7Vで４秒，−0.6Vで１秒の周期的に一定時間逆電圧が
加わる反転パルス電圧波形を与えた。表１は電気量（酸
化電流の積分値）を同一（10C/cm2）にし、電解酸化重
合によって得られる有機高分子の重量変化を、粒子を入
れないで得た高分子の重量を100とした場合、粒子を入
れ直流のみで得た高分子、粒子を入れ反転パルス電圧を
与へ電解し得た高分子について重量を示したものであ
る。表から明らかなように反転パルス電圧を与へ電解し
得た高分子の重量が大きい事が分る。これは、電解液中
の粒子が陰分極した際に電極に引き寄せられると共に、
電極面で電荷ｅを受けとり、粒子内に電解液中のH+がト
ラップされ、粒子自身が絶縁体から導体へ変化し、次ぎ
に、この状態で陽分極が起きると電極面と粒子面で有機
モノマーの酸化が進行するため、実施例１〜３の方法以
上に効率よく粒子が有機高分子の中に入ったためと考え
られる。Example 4 As the particles to be contained in the electrolytic solution, molybdenum oxide having a diameter of 30 μm or less was used, and electrolytic polymerization was performed using the apparatus of Example 1. At this time, the voltage applied to the electrode for electrolytic polymerization is +
An inversion pulse voltage waveform was applied in which a reverse voltage was applied periodically for a fixed time of 0.7 V for 4 seconds and -0.6 V for 1 second. Table 1 shows that the quantity of electricity (integrated value of oxidation current) is the same (10 C / cm 2 ) and the weight change of the organic polymer obtained by electrolytic oxidation polymerization is 100 when the weight of the polymer obtained without particles is 100%. In this case, the weight is shown for the polymer obtained by putting the particles into it only by direct current, and the polymer obtained by putting the particles in and applying electrolysis to the reverse pulse voltage. As is clear from the table, it is found that the weight of the polymer that has been electrolyzed by applying the reverse pulse voltage is large. This is because when the particles in the electrolyte are negatively polarized, they are attracted to the electrode,
The charge e is received on the electrode surface, H + in the electrolytic solution is trapped inside the particle, the particle itself changes from an insulator to a conductor, and then when anodic polarization occurs in this state, the organic surface is formed on the electrode surface and the particle surface. It is considered that the particles entered the organic polymer more efficiently than the method of Examples 1 to 3 because the oxidation of the monomer proceeded.
尚、本発明では、微粒子粒子を電解液中に分散し電解
する方法のみを示したが、電極表面に粒子を沈降せしめ
たり、多量の粒子に電解液を湿潤せしめた中に試料電極
を挿入し電解合成することによって、多量の粒子を高分
子内に混入させうることは明示しないまでも、本発明の
範囲に属するものである。更に、本発明では、タングス
テン、酸化タングステン（WO3，WO2）酸化モリブデンの
み微粉末粒子として例示したが、電解液に不溶な材料は
全て使用可能なことは明らかなものである。又、有機高
分子として、ポリピロールのみを例示したが、該材料の
みに限定されるものでなく、例えば、Ｎ−X4ルピロー
ル，チオフエン，アニリン，等、全て有機電解重合に用
いられるモノマーに適用しうるものである。又、使用す
る電解液も、有機溶媒に特に限定されるものではなく、
水系溶媒中からの有機電解重合にも適用しうるものであ
り、これらは全て、本発明の範囲に属することは云うま
でもない事である。 Incidentally, in the present invention, only the method of dispersing and electrolyzing fine particles in the electrolytic solution was shown, but the particles were allowed to settle on the electrode surface, or the sample electrode was inserted into a large amount of the particles wetted with the electrolytic solution. It is within the scope of the present invention, although it is not explicitly stated that a large amount of particles can be mixed into the polymer by electrolytic synthesis. Further, in the present invention, only tungsten and tungsten oxide (WO 3 , WO 2 ) molybdenum oxide are exemplified as the fine powder particles, but it is clear that any material insoluble in the electrolytic solution can be used. Further, although only polypyrrole is exemplified as the organic polymer, it is not limited only to the material, and for example, N-X4 lupyrrole, thiophene, aniline, etc. can be applied to all the monomers used in the organic electropolymerization. It is a thing. Further, the electrolytic solution used is not particularly limited to the organic solvent,
It can be applied to organic electropolymerization from an aqueous solvent, and it goes without saying that all of them belong to the scope of the present invention.
発明の効果 本発明によれば、有機高分子中に微粉末粒子を容易に
入れることができ、本発明の方法を用いて、種々の機能
を有した粒子を使う事が可能で各種機能センサー，電池
の容量の向上、スマートセンサー等、その応用展開技術
分野を拡大しうることに効果がある。Effects of the Invention According to the present invention, fine powder particles can be easily put in an organic polymer, and particles having various functions can be used by using the method of the present invention. It is effective in improving the capacity of the battery and expanding the field of application and development of its applications such as smart sensors.
第１図は、本発明の一実施例における電解装置を示す断
面図、第２図は、高分子中の粒子のESCAによる分析結果
を示すグラフである。 １……電解槽、３……試料電極、４……参照電極、５…
…対向電極、６……電解液、７……微粉末粒子。FIG. 1 is a cross-sectional view showing an electrolyzer in one embodiment of the present invention, and FIG. 2 is a graph showing the results of ESCA analysis of particles in a polymer. 1 ... electrolytic cell, 3 ... sample electrode, 4 ... reference electrode, 5 ...
... Counter electrode, 6 ... electrolyte, 7 ... fine powder particles.
Claims (2)
させ、該電解液中に電極を押入し、電解重合することに
より、微粉末を含有した有機高分子を得ることを特徴と
する有機高分子の電解重合法。1. An organic polymer containing fine powder is obtained by including fine powder in an electrolytic solution used for electrolytic polymerization, pressing an electrode into the electrolytic solution, and performing electrolytic polymerization. Electropolymerization of organic polymers.
として、周期的に一定時間、異なった電圧が加わる、反
転パルス電圧波形を用いた事を特徴とする特許請求範囲
第１項記載の有機高分子の電解重合法。2. An organic EL device according to claim 1, wherein an inverted pulse voltage waveform in which different voltages are periodically applied for a fixed time is used as a voltage waveform applied to the electrode for electrolytic polymerization. Polymer electropolymerization method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61023220A JPH0830107B2 (en) | 1986-02-05 | 1986-02-05 | Electropolymerization of organic polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61023220A JPH0830107B2 (en) | 1986-02-05 | 1986-02-05 | Electropolymerization of organic polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62181326A JPS62181326A (en) | 1987-08-08 |
| JPH0830107B2 true JPH0830107B2 (en) | 1996-03-27 |
Family
ID=12104568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61023220A Expired - Lifetime JPH0830107B2 (en) | 1986-02-05 | 1986-02-05 | Electropolymerization of organic polymers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0830107B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013057103A (en) * | 2011-09-08 | 2013-03-28 | Tokyo Institute Of Technology | Method for manufacturing polymer film, conductive substrate with polymer film, and electropolymerization apparatus for manufacturing polymer film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5975943A (en) * | 1982-10-25 | 1984-04-28 | Showa Denko Kk | Production of electrically conductive polymer composition |
-
1986
- 1986-02-05 JP JP61023220A patent/JPH0830107B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013057103A (en) * | 2011-09-08 | 2013-03-28 | Tokyo Institute Of Technology | Method for manufacturing polymer film, conductive substrate with polymer film, and electropolymerization apparatus for manufacturing polymer film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62181326A (en) | 1987-08-08 |
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