JPS6139982B2 - - Google Patents
Info
- Publication number
- JPS6139982B2 JPS6139982B2 JP8640279A JP8640279A JPS6139982B2 JP S6139982 B2 JPS6139982 B2 JP S6139982B2 JP 8640279 A JP8640279 A JP 8640279A JP 8640279 A JP8640279 A JP 8640279A JP S6139982 B2 JPS6139982 B2 JP S6139982B2
- Authority
- JP
- Japan
- Prior art keywords
- acetylene polymer
- acetylene
- doped
- polymer film
- electrical conductivity
- 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
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 50
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 28
- -1 platinum group metal complex Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 229920006254 polymer film Polymers 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- QVGRURMQPVFYBL-UHFFFAOYSA-N (2,3,4-triphenylcyclobuta-1,3-dien-1-yl)benzene Chemical compound C1=CC=CC=C1C1=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 QVGRURMQPVFYBL-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- LYXFCGCYJQCSRL-UHFFFAOYSA-N OOSO Chemical compound OOSO LYXFCGCYJQCSRL-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明はドープしたアセチレン重合体の製造法
に関する。更に詳しくは、本発明は、白金族金属
化合物によりドープしたアセチレン重合体の製造
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for making doped acetylene polymers. More particularly, the present invention relates to a method for making acetylene polymers doped with platinum group metal compounds.
アセチレン重合体は電気伝導度が10-5Ω-1cm-1
〜10-9Ω-1cm-1のオーダーの半導体ないしは絶縁
体である（Makromol.Chem.175巻1565頁（1978
年）。このものの電気伝導度を高める方法として
従来いくつかの方法が提案されている。例えばJ.
Amer.Chem.Soc.、100巻1013頁（1978年）に
は、アセチレン重合体フイルムに対し、HBr.
Cl2、Br2、I2、ICl、IBr、AsF5、Naなどをドー
パントとして用いてドープすることによつてアセ
チレン重合体の電気伝導度を増大させる方法が述
べられている。これらのドーパントのうちでも最
も有効なものはI2、AsF5などであり、その際に
得られる電気伝導度は最高で102Ω-1cm-1のオー
ダーのものである。また、J.Chem.Soc.Chem.
Comm.489頁、1066頁（1978年）には、それぞれ
銀塩（AgBF4、AgClO4）やFSO2OOSO2Fを用い
てドープする方法が提案されている。前者の場
合、電気伝導度は100Ω-1cm-1のオーダーのもの
が得られ、後者の場合は102Ω-1cm-1のオーダー
のものが得られている。上記試薬によるドーピン
グは、アセチレン重合体が不溶性であるので、ガ
ス状で試薬をアセチレン重合体に浸透させるか、
あるいは試薬を溶媒に溶かした状態でアセチレン
重合体に浸透させる方法により行なわれている。 Acetylene polymer has an electrical conductivity of 10 -5 Ω -1 cm -1
It is a semiconductor or insulator of the order of ~10 -9 Ω -1 cm -1 (Makromol. Chem. Vol. 175, p. 1565 (1978
Year). Several methods have been proposed to increase the electrical conductivity of this material. For example, J.
Amer.Chem.Soc., Vol. 100, p. 1013 (1978) describes HBr for acetylene polymer films.
A method is described for increasing the electrical conductivity of acetylene polymers by doping them with Cl 2 , Br 2 , I 2 , ICl, IBr, AsF 5 , Na, etc. as dopants. The most effective of these dopants are I 2 , AsF 5 , etc., with electrical conductivities of the order of 10 2 Ω −1 cm −1 at most. Also, J.Chem.Soc.Chem.
Comm. p. 489 and p. 1066 (1978) propose doping methods using silver salts (AgBF 4 , AgClO 4 ) and FSO 2 OOSO 2 F, respectively. In the former case, an electrical conductivity of the order of 10 0 Ω -1 cm -1 was obtained, and in the latter case, an electrical conductivity of the order of 10 2 Ω -1 cm -1 was obtained. Doping with the above reagent can be done by infiltrating the acetylene polymer with the reagent in gaseous form, since the acetylene polymer is insoluble;
Alternatively, it is carried out by a method in which a reagent is dissolved in a solvent and permeated into an acetylene polymer.
本発明者等はアセチレン重合体をドープする方
法について種々研究の結果、従来技術に類をみな
い遷移金属錯体の配位子交換反応を用いて白金族
金属化合物によりドープしたアセチレン重合体を
得ることに成功した。したがつて本発明は白金族
金属化合物によりドープしたアセチレン重合体の
製造法を提供するものである。 As a result of various studies on methods for doping acetylene polymers, the present inventors have found that an acetylene polymer doped with a platinum group metal compound can be obtained using a ligand exchange reaction of a transition metal complex, which is unprecedented in the prior art. succeeded in. Accordingly, the present invention provides a method for making acetylene polymers doped with platinum group metal compounds.
本発明は以下に掲げる如き特徴的利点を有する
ものであるので、その応用分野は広く、産業上極
めて有用なものである。 Since the present invention has the following characteristic advantages, its application fields are wide and it is extremely useful industrially.
１ 本発明方法において使用するドーパントは腐
蝕性、毒性、揮発性がないので、ドーピングの
処理操作にとり著しい利点となるほかドープし
たアセチレン重合体も性能上安定なものとな
る。1 The dopant used in the process of the present invention is not corrosive, toxic, or volatile, which is a significant advantage for the doping process and also makes the doped acetylene polymer stable in terms of performance.
２ 本発明方法においては、目的とするドープし
たアセチレン重合体の電気伝導度を任意の所望
のオーダーに制御することができる。2 In the method of the present invention, the electrical conductivity of the target doped acetylene polymer can be controlled to any desired order.
３ 本発明方法により得られるドープしたアセチ
レン重合体は太陽電池、各種センサーなどの有
機半導体材料として優れた性能を有する。3. The doped acetylene polymer obtained by the method of the present invention has excellent performance as an organic semiconductor material for solar cells, various sensors, etc.
以下に本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明方法は、アセチレン重合体を白金族金属
錯体の有機溶媒溶液で処理することを特徴とする
ものであるが、本発明で用いられる白金族金属錯
体とは、オレフイン類の置換反応に活性な白金族
金属錯体であり、例えば（PhCN）2PdCl2、
（COD）PdCl2、〔（C2H4）PdCl2〕2、（Ph4C4）
PdCl2、（COD）PtCl2、Ｋ〔PtCl3（C2H4）〕
H2O、〔Pt（C2H4）Cl2〕2、（PhCN）2PtCl2、
〔（C2H4）2RhCl〕、Ru（COD）Cl2
（式中のCODは１・５−シクロオクタジエンであ
りPh4C4はテトラフエニルシクロブタジエンであ
る）などが挙げられる。 The method of the present invention is characterized by treating an acetylene polymer with a solution of a platinum group metal complex in an organic solvent. platinum group metal complexes, such as (PhCN) 2 PdCl 2 ,
( COD ) PdCl2 , [( C2H4 ) PdCl2 ] 2 , ( Ph4C4 )
PdCl 2 , (COD) PtCl 2 , K [PtCl 3 (C 2 H 4 )]
H2O , [Pt( C2H4 )Cl2 ] 2 , ( PhCN) 2PtCl2 ,
[( C2H4 ) 2RhCl ], Ru( COD ) Cl2 (in the formula, COD is 1,5-cyclooctadiene and Ph4C4 is tetraphenylcyclobutadiene), and the like.
パラジウム錯体、例えば（PhCN）2PdCl2、
〔（C2H4）PdCl2〕2は本発明において使用する白
金族金属錯体として好ましい金属錯体である。使
用する溶媒としては、使用する金属錯体が溶けて
均質になるものであれば全て用いることができ
る。溶媒の例としては、ベンゼン、トルエン、メ
チレンクロリド、クロロホルム、アセトン、テト
ラヒドロフランなどがあげられる。原料アセチレ
ン重合体は粉末状、膜状、繊維状いずれでも使用
可能であり、特定されない。 Palladium complexes, e.g. (PhCN) 2 PdCl 2 ,
[(C 2 H 4 )PdCl 2 ] 2 is a preferred metal complex as the platinum group metal complex used in the present invention. Any solvent can be used as long as it dissolves the metal complex used and becomes homogeneous. Examples of solvents include benzene, toluene, methylene chloride, chloroform, acetone, and tetrahydrofuran. The raw material acetylene polymer can be used in the form of powder, film, or fiber, and is not specified.
本発明におけるドーピング処理は、アセチレン
重合体が酸素に対して不安定であるため不活性ガ
スの雰囲気中、例えば、窒素またはアルゴン雰囲
気中で行なうことが好ましく、上記金属錯体の均
質溶液をつくり、これにアセチレン重合体を浸漬
することにより行うことができる。溶液の使用濃
度は用いる錯体の溶解度により異なるが、濃度の
大きい溶液を用いるほど短時間でドープされる金
属化合物の割合が多くなる傾向がある。原料アセ
チレン重合体の浸漬時間は用いる溶液の濃度およ
びドーピング処理の温度により変えられる。浸漬
処理は通常、室温で行なうが錯体が分解しない程
度に加熱加温してもよい。浸漬処理後のアセチレ
ン重合体は浸漬に用いたと同じ溶媒で洗浄した後
溶媒を除去する。これらの処理は、不活性ガス雰
囲気中または真空下で行なうことが好ましい。こ
うして得られたドープしたアセチレン重合体の電
気伝導度はドープされた金属の種類と量に依存す
るが、この電気伝導度は４−採針法などにより測
定することができる。 The doping treatment in the present invention is preferably carried out in an inert gas atmosphere, such as a nitrogen or argon atmosphere, since the acetylene polymer is unstable to oxygen. This can be done by immersing the acetylene polymer in the water. Although the concentration of the solution used varies depending on the solubility of the complex used, there is a tendency that the higher the concentration of the solution used, the greater the proportion of the metal compound doped in a short time. The immersion time of the raw acetylene polymer varies depending on the concentration of the solution used and the temperature of the doping treatment. The dipping treatment is usually carried out at room temperature, but may be heated to an extent that the complex does not decompose. After the immersion treatment, the acetylene polymer is washed with the same solvent used for immersion, and then the solvent is removed. These treatments are preferably performed in an inert gas atmosphere or under vacuum. The electrical conductivity of the doped acetylene polymer thus obtained depends on the type and amount of the doped metal, but this electrical conductivity can be measured by the 4-needle sampling method or the like.
本発明者がPd錯体によりドープした膜状アセ
チレン重合体のESCA（Electron Spectroscopy
for Chemical Analysis）の測定を行なつたとこ
ろ、価のPdのみが検出された。このことから
ドープしたアセチレン重合体の電気伝導度はPd
化合物がアセチレン重合体にドープされた結果、
増大したもので、錯体の分解により析出したPd
金属が伝導に関与したのではないことがわかる。
なお、ドープしたアセチレン重合体も酸素に対し
て不安定であるため、不活性ガス中で取扱うこと
が好ましい。 The present inventor conducted an ESCA (Electron Spectroscopy) study of a film-like acetylene polymer doped with a Pd complex.
When measurements were carried out (for Chemical Analysis), only valent Pd was detected. From this, the electrical conductivity of the doped acetylene polymer is Pd
As a result of the compound being doped into the acetylene polymer,
Pd precipitated due to decomposition of the complex.
It can be seen that the metal was not involved in conduction.
Note that since the doped acetylene polymer is also unstable to oxygen, it is preferable to handle it in an inert gas.
以下に本発明の実施例を掲げるが本発明は以下
の実施例に限定されるものではない。なお、実施
例中で使用されているアセチレン重合体フイルム
は次の如くして調製された。 Examples of the present invention are listed below, but the present invention is not limited to the following examples. The acetylene polymer film used in the examples was prepared as follows.
アセチレン重合体フイルムの調製
窒素雰囲気下で内容積500mlのガラス容器に1.7
mlのチタニウムテトラブトキサイドを加え30mlの
トルエンに溶かし、2.7mlのトリエチルアルミニ
ウムを撹拌しながら加えて反応させた。この容器
を重合装置にとりつけ触媒溶液を液体窒素で凝固
させ真空ポンプで容器中の窒素を抜きとつた。室
温にもどし溶液中に溶解していた窒素を気化させ
た後再び液体窒素で凝固させ脱気した。次いで容
器をドライアイス−メタノール混合物の温度に保
ち、静止したまゝでガス溜に保存しておいた精製
アセチレンを大気圧以下でこの容器に導入した。Preparation of acetylene polymer film 1.7 in a glass container with an internal volume of 500 ml under nitrogen atmosphere
ml of titanium tetrabutoxide was added and dissolved in 30 ml of toluene, and 2.7 ml of triethylaluminum was added with stirring to cause a reaction. This container was attached to a polymerization apparatus, the catalyst solution was solidified with liquid nitrogen, and the nitrogen in the container was removed using a vacuum pump. After returning the solution to room temperature and vaporizing the nitrogen dissolved in the solution, it was again solidified with liquid nitrogen and degassed. The vessel was then maintained at the temperature of the dry ice-methanol mixture, and purified acetylene, which had been kept stationary in a gas reservoir, was introduced into the vessel at subatmospheric pressure.
直ちに溶液表面で重合が起り、フイルム状アセ
チレン重合体が生成した。アセチレン導入後30分
で容器を重合装置からはずし窒素を導入した。窒
素雰囲気下で触媒溶液を注射器で除いた後、続け
て乾燥、脱気したトルエンで十分洗浄した。次に
注射器でトルエンを除き真空下で乾燥し、アセチ
レン重合体フイルムを得た。 Polymerization immediately occurred on the surface of the solution, producing a film-like acetylene polymer. Thirty minutes after the introduction of acetylene, the container was removed from the polymerization apparatus and nitrogen was introduced. After removing the catalyst solution with a syringe under a nitrogen atmosphere, the solution was thoroughly washed with dried and degassed toluene. Next, toluene was removed using a syringe and the mixture was dried under vacuum to obtain an acetylene polymer film.
このアセチレン重合体フイルムの電気伝導度は
10-8Ω-1cm-1であつた。 The electrical conductivity of this acetylene polymer film is
It was 10 -8 Ω -1 cm -1 .
実施例 １
0.2ｇの〔（C2H4）PdCl2〕2を乾燥、脱酸素した
クロロホルム20mlに溶解した溶液にアセチレン重
合体フイルムを浸し、24時間室温で放置する。そ
の後、このアセチレン重合体フイルムを別の容器
に移し、クロロホルムで洗浄し、真空乾燥する。
こうして得られたドープしたアセチレン重合体フ
イルムの電気伝導度を４−採針法で測定すると３
×10-2Ω-1cm-1であつた。Example 1 An acetylene polymer film is immersed in a solution of 0.2 g of [(C 2 H 4 )PdCl 2 ] 2 dissolved in 20 ml of dry, deoxygenated chloroform and left at room temperature for 24 hours. Thereafter, this acetylene polymer film is transferred to another container, washed with chloroform, and vacuum dried.
The electrical conductivity of the doped acetylene polymer film thus obtained was 3 when measured by the 4-needle method.
×10 -2 Ω -1 cm -1 .
なお、本実施例における操作は、アセチレン重
合体を大気に晒さないように、全て窒素雰囲気下
において行なつた。以下の実施例においても同様
である。 The operations in this example were all carried out under a nitrogen atmosphere so as not to expose the acetylene polymer to the atmosphere. The same applies to the following examples.
実施例 ２
0.1ｇの（PhCN）2PdCl2を乾燥、脱酸素したメ
チレンクロリド20mlに溶解した溶液に、アセチレ
ン重合体フイルムを浸し、室温で24時間放置す
る。その後このアセチレン重合体フイルムを別の
容器に移し、メチレンクロリドで洗浄し、真空乾
燥する。こうして得られたドープしたアセチレン
重合体フイルムの電気伝導度は３×10-3Ω-1cm-1
であつた。Example 2 An acetylene polymer film is immersed in a solution of 0.1 g of (PhCN) 2 PdCl 2 dissolved in 20 ml of dry, deoxygenated methylene chloride and left at room temperature for 24 hours. Thereafter, this acetylene polymer film is transferred to another container, washed with methylene chloride, and vacuum dried. The electrical conductivity of the doped acetylene polymer film thus obtained is 3×10 -3 Ω -1 cm -1
It was hot.
実施例 ３
0.1ｇ（PhCN）2PtCl2を乾燥、脱酸素した20ml
のメチレンクロリドに溶解した溶液にアセチレン
重合体フイルムを浸し、24時間室温に放置する。
その後このアセチレン重合体フイルムをメチレン
クロリドで洗浄し真空乾燥する。こうして得られ
たドープしたアセチレン重合体フイルムの電気伝
導度は、７×10-5Ω-1cm-1であつた。Example 3 20ml of dried and deoxygenated 0.1g (PhCN) 2 PtCl 2
An acetylene polymer film is immersed in a solution of methylene chloride and left at room temperature for 24 hours.
Thereafter, this acetylene polymer film is washed with methylene chloride and vacuum dried. The electrical conductivity of the doped acetylene polymer film thus obtained was 7×10 -5 Ω -1 cm -1 .
実施例 ４
0.1ｇの〔（C2H4）2RhCl〕を乾燥、脱酸素した
20mlのメチレンクロリドに溶解した溶液にアセチ
レン重合体フイルムを浸し、24時間室温に放置す
る。その後このアセチレン重合体フイルムをメチ
レンクロリドで洗浄し、真空乾燥する。Example 4 0.1 g of [(C 2 H 4 ) 2 RhCl] was dried and deoxidized.
Soak the acetylene polymer film in a solution dissolved in 20 ml of methylene chloride and leave at room temperature for 24 hours. Thereafter, this acetylene polymer film is washed with methylene chloride and vacuum dried.
こうして得られたドープしたアセチレン重合体
フイルムの電気伝導度は５×10-5Ω-1cm-1であつ
た。 The electrical conductivity of the doped acetylene polymer film thus obtained was 5×10 -5 Ω -1 cm -1 .
実施例 ５
0.1ｇのRu（COD）Cl2を乾燥、脱酸素したク
ロロホルム20mlに溶かした溶液にアセチレン重合
体フイルムを浸す。室温に24時間放置した後、こ
のアセチレン重合体フイルムをクロロホルムで洗
浄し真空乾燥する。こうして得られたドープした
アセチレン重合体フイルムの電気伝導度は６×
10-5Ω-1cm-1であつた。Example 5 An acetylene polymer film is immersed in a solution of 0.1 g of Ru(COD)Cl 2 dissolved in 20 ml of dry, deoxygenated chloroform. After being left at room temperature for 24 hours, the acetylene polymer film was washed with chloroform and dried in vacuum. The electrical conductivity of the doped acetylene polymer film thus obtained is 6×
It was 10 -5 Ω -1 cm -1 .
Claims (1)
応に活性のある白金族金属錯体の有機溶媒溶液で
処理することを特徴とするドープしたアセチレン
重合体の製造法。1. A method for producing a doped acetylene polymer, which comprises treating the acetylene polymer with an organic solvent solution of a platinum group metal complex active in a substitution reaction with olefins.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8640279A JPS5611939A (en) | 1979-07-10 | 1979-07-10 | Production of doped acetylenic polymer |
| EP80103857A EP0022271B1 (en) | 1979-07-10 | 1980-07-07 | Doped polyacetylenes and their production |
| DE8080103857T DE3069926D1 (en) | 1979-07-10 | 1980-07-07 | Doped polyacetylenes and their production |
| US06/166,995 US4349664A (en) | 1979-07-10 | 1980-07-09 | Doped acetylene polymer and process for production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8640279A JPS5611939A (en) | 1979-07-10 | 1979-07-10 | Production of doped acetylenic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5611939A JPS5611939A (en) | 1981-02-05 |
| JPS6139982B2 true JPS6139982B2 (en) | 1986-09-06 |
Family
ID=13885864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8640279A Granted JPS5611939A (en) | 1979-07-10 | 1979-07-10 | Production of doped acetylenic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5611939A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05315769A (en) * | 1992-05-06 | 1993-11-26 | Fujitsu Ten Ltd | Structure for fixation of cord of electrified product |
| JPH0546245Y2 (en) * | 1987-10-27 | 1993-12-03 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2508914B1 (en) * | 1981-07-03 | 1986-08-29 | Thomson Csf | CONDUCTIVE POLYACETYLENE MATERIAL WITH HIGH STABILITY AND MANUFACTURING METHOD THEREOF |
-
1979
- 1979-07-10 JP JP8640279A patent/JPS5611939A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0546245Y2 (en) * | 1987-10-27 | 1993-12-03 | ||
| JPH05315769A (en) * | 1992-05-06 | 1993-11-26 | Fujitsu Ten Ltd | Structure for fixation of cord of electrified product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5611939A (en) | 1981-02-05 |
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