JPH0796609B2 - Conductive composition - Google Patents
Conductive compositionInfo
- Publication number
- JPH0796609B2 JPH0796609B2 JP61078377A JP7837786A JPH0796609B2 JP H0796609 B2 JPH0796609 B2 JP H0796609B2 JP 61078377 A JP61078377 A JP 61078377A JP 7837786 A JP7837786 A JP 7837786A JP H0796609 B2 JPH0796609 B2 JP H0796609B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive composition
- polymer
- present
- conductivity
- heterocyclic compound
- 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
- 239000000203 mixture Substances 0.000 title claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- TULWUZJYDBGXMY-UHFFFAOYSA-N tellurophene Chemical compound [Te]1C=CC=C1 TULWUZJYDBGXMY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- 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〕 本発明は新規な導電性組成物に関する。さらに詳しく
は、特定のドーパントをドープしてなる安定性の高い複
素環式化合物系導電性組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel conductive composition. More specifically, it relates to a highly stable heterocyclic compound-based conductive composition obtained by doping a specific dopant.
複素環式化合物重合体は適当なドーパントをドープする
ことにより高導電体となり、またドーピング、脱ドーピ
ングが可能なことから一次電池，二次電池，太陽電池、
光導電材料や種々の電子デバイス材料の分野で利用可能
である。The heterocyclic compound polymer becomes a high electric conductor by doping with a suitable dopant, and since it can be doped and dedoped, it can be used for primary batteries, secondary batteries, solar cells,
It can be used in the fields of photoconductive materials and various electronic device materials.
酸素族元素を含む複素環式化合物系重合体の製造方法と
しては、電解酸化重合法及び酸化剤を用いた化学的酸化
重合法の２通りが公知である（たとえば、G.Tourillon
J.Phys.Chem.,87 2289（1983））。As a method for producing a heterocyclic compound-based polymer containing an oxygen group element, there are known two methods, an electrolytic oxidative polymerization method and a chemical oxidative polymerization method using an oxidizing agent (for example, G. Tourillon.
J. Phys. Chem., 87 2289 (1983)).
しかしながら、いずれの方法で得られる重合体もドーパ
ントをドープした状態が不安定であるため、溶媒での洗
浄や単に空気中に保持しておくだけで急速に脱ドープ現
象が起こり導電性が悪くなつてしまうという問題があつ
た。However, the polymer obtained by any of the methods is unstable in the state of being doped with a dopant, and therefore the dedoping phenomenon occurs rapidly and the conductivity deteriorates only by washing with a solvent or simply keeping it in the air. There was a problem that it would end up.
本発明者らは上記問題点を解決するため鋭意検討したと
ころ、特定のドーパントをドーピングすることによつて
安定な導電性を有する導電性組成物が得られることを見
い出し、本発明を完成した。The inventors of the present invention have made extensive studies to solve the above problems, and have found that a conductive composition having stable conductivity can be obtained by doping a specific dopant, and have completed the present invention.
すなわち、本発明は、２価以上の価数を有し、かつイオ
ンの直径が10Å以上である嵩高いアニオンをドープして
なる安定な導電性を有する酸素族元素を含む複素環式化
合物系導電性組成物である。That is, the present invention is a heterocyclic compound-based conductive material containing a stable conductive oxygen group element having a valence of two or more and a bulky anion having an ion diameter of 10Å or more. It is a sex composition.
本発明における酸素族元素を含む複素環式化合物系重合
体としては、フラン、チオフェン、セレノフェン、テル
ロフェン及びそれらの3,4位に置換基を有する誘導体等
の重合体が挙げられる。Examples of the heterocyclic compound-based polymer containing an oxygen group element in the present invention include polymers such as furan, thiophene, selenophene, tellurophene, and derivatives thereof having a substituent at the 3,4 position.
本発明において用いられる２価以上の価数を有し、かつ
イオンの直径が10Å以上である嵩高いアニオンとは、た
とえばデカクロデカボレート（B10Cl10 2-）、ドデカク
ロロドデカボレート（B12Cl12 2-）など、ポリスルホン
酸ナトリウム、ポリビニル硫酸カリウムなどのアニオン
性高分子化合物のアニオンなどが挙げられる。Bulky anions having a valence of 2 or more and an ion diameter of 10 Å or more used in the present invention include, for example, decaclodecaborate (B 10 Cl 10 2- ), dodecachlorododecaborate (B 12 Cl 12 2- ) and the like, and anions of anionic polymer compounds such as sodium polysulfonate and potassium polyvinyl sulfate.
本発明の導電性組成物を製造する方法としては、公知の
方法が利用できる。たとえば、電解重合法では、上記の
アニオンを有する塩を支持電解質として用いて、電解酸
化することにより製造することができる。また通常の方
法で得られた重合体に上記アニオンを電気化学的にドー
プすることによつても得られる。一方、化学的酸化重合
法では、上記アニオンの存在下、酸化重合することによ
り重合体中にアニオンが取り込まれて、導電性組成物が
得られる。As a method for producing the conductive composition of the present invention, known methods can be used. For example, in the electrolytic polymerization method, it can be produced by electrolytically oxidizing a salt having the above anion as a supporting electrolyte. It can also be obtained by electrochemically doping the polymer obtained by a usual method with the above anion. On the other hand, in the chemical oxidative polymerization method, the anion is incorporated into the polymer by oxidative polymerization in the presence of the above anion to obtain a conductive composition.
このようにして得られる導電性組成物は、アルコールな
どの溶媒で洗浄した後、空気中に放置しておいても安定
な導電性を示す。The electroconductive composition thus obtained shows stable electroconductivity even if it is left in the air after being washed with a solvent such as alcohol.
以下、実施例により、さらに本発明を説明する。 The present invention will be further described below with reference to examples.
実施例１ 陽極に導電性ガラス（ネサガラス）、陽極にニッケル板
をそれぞれ電極とする容器を窒素ボックス中に入れ、支
持電解質として、リチウムデカクロロデカボレート（Li
2B10Cl10）1gを入れニトロベンゼン50mlに溶解した。さ
らにチオフェン1gを入れ、室温で上記電極間に10Vの印
加電圧をかけて、30分間電解酸化したところ、陽極上に
黒色の重合体フィルムが生成した。Example 1 A container having a conductive glass (Nesa glass) as an anode and a nickel plate as an anode was placed in a nitrogen box, and lithium decachlorodecaborate (Li) was used as a supporting electrolyte.
2 B 10 Cl 10 ) 1 g was added and dissolved in 50 ml of nitrobenzene. Further, 1 g of thiophene was added, and an applied voltage of 10 V was applied between the electrodes at room temperature to carry out electrolytic oxidation for 30 minutes, whereby a black polymer film was formed on the anode.
メタノール洗浄後、一昼夜真空乾燥し、その後４端子法
で該黒色の重合体フィルムの電気伝導度を測定したとこ
ろ、3.3S/cmであつた。After washing with methanol, it was vacuum dried for a whole day and night, and then the electrical conductivity of the black polymer film was measured by a four-terminal method to find that it was 3.3 S / cm.
このサンプルを空気中で260℃で３時間処理した後の電
気伝導度は1.2S/cmであつた。The electrical conductivity of this sample was 1.2 S / cm after it was treated in air at 260 ° C. for 3 hours.
比較例１ 比較のため、支持電解質としてホウフッ化リチウム（Li
BF4）を用いた以外は実施例１同様の操作で合成した重
合体の導電率は9.8S/cmであり、260℃で３時間空気中で
熱処理したものの電気伝導度は２×10-7S/cmであつた。Comparative Example 1 For comparison, lithium borofluoride (Li) was used as a supporting electrolyte.
The polymer synthesized in the same manner as in Example 1 except that BF 4 ) was used had an electric conductivity of 9.8 S / cm and an electric conductivity of 2 × 10 −7 after heat treatment in air at 260 ° C. for 3 hours. It was S / cm.
実施例２ 支持電解質としてリチウムドデカクロロドデカボレート
（Li2B12Cl12）を用いる以外は実施例１と同様にして合
成した重合体の電気伝導度は4.8S/cmであつた。このサ
ンプルを260℃で３時間熱処理した後の電気伝導度は1.8
S/cmであつた。Example 2 A polymer synthesized in the same manner as in Example 1 except that lithium dodecachlorododecaborate (Li 2 B 12 Cl 12 ) was used as a supporting electrolyte had an electric conductivity of 4.8 S / cm. The electrical conductivity of this sample is 1.8 after heat treatment at 260 ℃ for 3 hours.
It was S / cm.
実施例３ チオフェンの代わりにセレノフェンを用いる以外は実施
例１と同様の方法で合成した重合体の電気伝導度は２×
10-4S/cmであり、260℃で３時間熱処理した後の電気伝
導度は７×10-5S/cmであつた。Example 3 The electrical conductivity of the polymer synthesized in the same manner as in Example 1 except that selenophene was used instead of thiophene was 2 ×.
The electric conductivity was 10 −4 S / cm, and the electric conductivity after heat treatment at 260 ° C. for 3 hours was 7 × 10 −5 S / cm.
本発明の導電性組成物は嵩高いアニオンをドープしてい
るので、極めて安定した導電性を有しており、一次電
池、二次電池、太陽電池、光導電材種々の電子デバイス
材料等に有効に用いうるものであり、その工業的価値は
きわめて高い。Since the conductive composition of the present invention is doped with a bulky anion, it has extremely stable conductivity and is effectively used for primary batteries, secondary batteries, solar cells, photoconductive materials, various electronic device materials, and the like. It can be used and its industrial value is extremely high.
Claims (1)
が10Å以上である嵩高いアニオンをドープしてなる安定
な導電性を有する酸素族元素を含む複素環式化合物系導
電性組成物。1. A heterocyclic compound-based electroconductivity containing an oxygen group element having a stable electroconductivity, which is obtained by doping a bulky anion having a valence of 2 or more and an ion diameter of 10 Å or more. Composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61078377A JPH0796609B2 (en) | 1986-04-07 | 1986-04-07 | Conductive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61078377A JPH0796609B2 (en) | 1986-04-07 | 1986-04-07 | Conductive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62236822A JPS62236822A (en) | 1987-10-16 |
| JPH0796609B2 true JPH0796609B2 (en) | 1995-10-18 |
Family
ID=13660326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61078377A Expired - Lifetime JPH0796609B2 (en) | 1986-04-07 | 1986-04-07 | Conductive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796609B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6162521A (en) * | 1984-09-03 | 1986-03-31 | Res Dev Corp Of Japan | Method for manufacturing conductive polymer |
-
1986
- 1986-04-07 JP JP61078377A patent/JPH0796609B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62236822A (en) | 1987-10-16 |
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