JPH02269107A - Production of polyacetylene - Google Patents
Production of polyacetyleneInfo
- Publication number
- JPH02269107A JPH02269107A JP9017589A JP9017589A JPH02269107A JP H02269107 A JPH02269107 A JP H02269107A JP 9017589 A JP9017589 A JP 9017589A JP 9017589 A JP9017589 A JP 9017589A JP H02269107 A JPH02269107 A JP H02269107A
- Authority
- JP
- Japan
- Prior art keywords
- titanate
- ziegler
- polyacetylene
- tetra
- acetylene
- 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.)
- Granted
Links
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229920001197 polyacetylene Polymers 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 14
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 9
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- -1 alkyl titanate Chemical compound 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 2
- USJZIJNMRRNDPO-UHFFFAOYSA-N tris-decylalumane Chemical compound CCCCCCCCCC[Al](CCCCCCCCCC)CCCCCCCCCC USJZIJNMRRNDPO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 1
- ALTIIFLXIBXXCX-UHFFFAOYSA-N decylaluminum Chemical compound CCCCCCCCCC[Al] ALTIIFLXIBXXCX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- KUVXJBSVPBXHEK-UHFFFAOYSA-N octylaluminum Chemical compound CCCCCCCC[Al] KUVXJBSVPBXHEK-UHFFFAOYSA-N 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JVIKNVRZMNQFFL-UHFFFAOYSA-N tri(tetradecyl)alumane Chemical compound CCCCCCCCCCCCCC[Al](CCCCCCCCCCCCCC)CCCCCCCCCCCCCC JVIKNVRZMNQFFL-UHFFFAOYSA-N 0.000 description 1
- XBEXIHMRFRFRAM-UHFFFAOYSA-N tridodecylalumane Chemical compound CCCCCCCCCCCC[Al](CCCCCCCCCCCC)CCCCCCCCCCCC XBEXIHMRFRFRAM-UHFFFAOYSA-N 0.000 description 1
- NHADXUOUFVKVEB-UHFFFAOYSA-N trihexadecylalumane Chemical compound CCCCCCCCCCCCCCCC[Al](CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC NHADXUOUFVKVEB-UHFFFAOYSA-N 0.000 description 1
- FPTXIDMSUMCELA-UHFFFAOYSA-N trioctadecylalumane Chemical compound CCCCCCCCCCCCCCCCCC[Al](CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC FPTXIDMSUMCELA-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
- C08F38/02—Acetylene
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は機械特性、特に延伸性の優れたポリアセチレン
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing polyacetylene having excellent mechanical properties, particularly stretchability.
従来の技術
ポリアセチレンは一例として、アセチレンをトリエチル
アルミニウムとテトラブチルチタネートからなるチーグ
ラー・ナッタ触媒により重合して得られることが、一般
によく知られている。 （シ。BACKGROUND OF THE INVENTION It is generally well known that polyacetylene, for example, can be obtained by polymerizing acetylene using a Ziegler-Natta catalyst consisting of triethylaluminum and tetrabutyl titanate. (Sh.
ヤーナル ネ°リマー 号イエンス、 本゛リマー ケ
ミカル エテ゛イション （Ｊ、 Ｐａ１ｙ１． Ｓ
ｃ１．、 Ｐｏｌｙｍ、 Ｃｈｅｗ、 Ｅｄ、）、 ＋
２．１１．１９７４年）発明が解決しようとする課題
しかしながら、前記のチーグラー・ナッタ触媒により得
られるポリアセチレンは延伸性には限界があり、３〜５
倍程度のものしか知られていない。Yarnal Neremer Chemical Edition (J, Pa1y1.S)
c1. , Polym, Chew, Ed, ), +
2.11.1974) Problems to be Solved by the Invention However, the polyacetylene obtained by the Ziegler-Natta catalyst has a limit in stretchability, and
Only about twice as many are known.
前記チーグラー・ナッタ触媒とアセチレンガスとを反応
させる場合、反応前にあらかじめ不活性ガス中において
８０〜１５０℃でチーグラー拳ナツタ触媒を熱処理する
と、ややポリアセチレンの延伸性の増加がみられるが、
十分ではない。When the Ziegler-Natta catalyst and acetylene gas are reacted, if the Ziegler-Natta catalyst is heat-treated at 80 to 150°C in an inert gas before the reaction, the stretchability of the polyacetylene is slightly increased.
Not enough.
課題を解決するための手段
アセチレンをトリアルキルアルミニウムラアルキルチタ
ネートからなるチーグラー・ナッタ触媒により重合する
方法において、前記トリアルキルアルミニウムおよび前
記テトラアルキルチタネートが両方とも炭素数６以上の
ア゛ルキル基を持つチーグラー・ナッタ触媒を用いる。Means for Solving the Problems A method of polymerizing acetylene using a Ziegler-Natta catalyst consisting of a trialkylaluminum dialkyl titanate, wherein both the trialkylaluminum and the tetraalkyl titanate have an alkyl group having 6 or more carbon atoms. A Ziegler-Natta catalyst is used.
作用
炭素数６以上のアルキル基を持つトリアルキルアルミニ
ウムおよびテトラアルキルチタネートを用いることによ
り、チーグラー曇ナツタ触媒の活性が抑えられて、重合
が比較的おだやかに進み、緻密な構造を持つポリアセチ
レンができるので、延伸性が向上するものと考えられる
。By using trialkylaluminum and tetraalkyl titanate that have an alkyl group with an active carbon number of 6 or more, the activity of the Ziegler cloudy Natsuta catalyst is suppressed, polymerization proceeds relatively slowly, and polyacetylene with a dense structure can be produced. , it is thought that the stretchability is improved.
実施例
本発明でアセチレンの重合に用いるチーグラー・ナッタ
触媒は、トリアルキルアルミニウムとアルキルチタネー
トから構成され、トリアルキルアルミニウムあるいは、
アルキルチタネートが炭素数６以上のアルキル基を持つ
。Examples The Ziegler-Natta catalyst used in the polymerization of acetylene in the present invention is composed of trialkylaluminum and alkyl titanate, and trialkylaluminum or
The alkyl titanate has an alkyl group having 6 or more carbon atoms.
本発明で用いる炭素数６以上のアルキル基を持つトリア
ルキルアルミニウム例としては、 トリーｎ−ヘキシル
アルミニウム、トリーｎ−オクチルアルミニウム、トリ
ーｎ−デシルアルミニウム、トリーｎ−ドデシルアルミ
ニウム、トリーｎ−テトラデシルアルミニウム、トリー
ｎ−ヘキサデシルアルミニウム、トリーｎ−オクタデシ
ルアルミニウム等があげられる。Examples of trialkyl aluminum having an alkyl group having 6 or more carbon atoms used in the present invention include tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum, tri-n-dodecyl aluminum, and tri-n-tetradecyl aluminum. , tri-n-hexadecylaluminum, tri-n-octadecylaluminum, and the like.
本発明で用いる炭素数６以上のアルキル基を持つアルキ
ルチタネートの例としては、テトラ−ｎ−へキシルチタ
ネート、テトラ−ｎ−オクチルチタネート、テトラ−ｎ
−デシルチタネート、テトラ−ｎ−ドデシルチタネート
、テトラ−ｎ−テトラデシルチタネート、テトラ−ｎ−
ヘキサデシルチタネート、テトラ−ｎ−オクタデシルチ
タネート等があげられる。Examples of alkyl titanates having an alkyl group having 6 or more carbon atoms used in the present invention include tetra-n-hexyl titanate, tetra-n-octyl titanate, and tetra-n-octyl titanate.
-decyl titanate, tetra-n-dodecyl titanate, tetra-n-tetradecyl titanate, tetra-n-
Examples include hexadecyl titanate and tetra-n-octadecyl titanate.
一般に、チーグラー・ナッタ触媒の溶媒としては、触媒
と反応しない炭化水素系溶媒か、芳香族系溶媒がよい。Generally, the solvent for the Ziegler-Natta catalyst is preferably a hydrocarbon solvent or an aromatic solvent that does not react with the catalyst.
次に具体的な例で本発明を説明する。Next, the present invention will be explained with specific examples.
実施例１
アルゴン雰囲気下でクメ７２．１ｍｌ、トリーｎ−ヘキ
シルアルミニウム３．５ｍ ｌ （０，１ｍｏｌ）、テ
トラ−ｎ−へキシルチタネー） ２．４ ｍ ｌ （０
，００５ｍｏｌ）を混合して調整した触媒溶液（以下の
実施例、比較例においても、トリアルキルアルミニラ及
びテトラアルキルチタネート量はそれぞれ０．０１ｍｏ
１１０．０（１５ｍｏ１とした）を１２０℃で２時間加
熱した後、４ｍｌを重合容器に入れ、真空ポンプで容器
中のアルゴン及びクメンを除去し、重合容器を回転させ
ながら、触媒溶液をガラス内壁に塗布した。重合容器内
の圧力が１０” Ｔｏｒｒ以下に下がった後、この重合
容器全体をドライアイス−エタノール混合冷媒で一７８
℃に冷却し、この温度に保ちながらアセチレンガスをこ
の重合容器に導入した。その時のガス圧は約ｆ１００Ｔ
ｏｒｒとなるようガス量を調製した。アセチレンガスの
導入と同時に溶液表面、及び容器内壁で重合が起こり、
ポリアセチレンフィルムの生成が見られる。４時間その
まま反応をつづけ、アセチレンガスを除き、重合容器内
をアルゴン雰囲気に戻した。アルゴン雰囲気下でポリア
セチレンフィルムをトルエンで洗浄した。洗浄は溶媒に
触媒の色（黒褐色）がつかなくなるまで繰り返した。洗
浄後ポリアセチレンフィルムを真空乾燥した。得られた
ポリアセチレンを１０Ｘ２０＋＊ｍに切取り、手動式の
延伸器でアルゴン雰囲気下、室温で延伸した。Example 1 Under an argon atmosphere, 72.1 ml of Kume, 3.5 ml (0.1 mol) of tri-n-hexylaluminum, 2.4 ml (0.1 mol) of tri-n-hexyl titanium)
, 005 mol)) (also in the following Examples and Comparative Examples, the amounts of trialkylaluminilla and tetraalkyl titanate were each 0.01 mol).
After heating 110.0 (15 mo1) at 120°C for 2 hours, 4 ml was put into a polymerization container, argon and cumene in the container were removed using a vacuum pump, and the catalyst solution was poured onto the glass inner wall while rotating the polymerization container. It was applied to. After the pressure inside the polymerization vessel was reduced to 10” Torr or less, the entire polymerization vessel was cooled with a dry ice-ethanol mixed refrigerant.
C. and, while maintaining this temperature, acetylene gas was introduced into the polymerization vessel. The gas pressure at that time is approximately f100T
The gas amount was adjusted so that it was orr. Simultaneously with the introduction of acetylene gas, polymerization occurs on the solution surface and the inner wall of the container.
Formation of polyacetylene film is observed. The reaction was continued for 4 hours, and the acetylene gas was removed, and the inside of the polymerization vessel was returned to an argon atmosphere. The polyacetylene film was washed with toluene under an argon atmosphere. Washing was repeated until the solvent no longer had the color of the catalyst (blackish brown). After washing, the polyacetylene film was vacuum dried. The obtained polyacetylene was cut into a size of 10×20+*m and stretched at room temperature under an argon atmosphere using a manual stretcher.
実施例２
実Ｍｌｉ例１のトリーｎ−ヘキシルアルミニウム３．５
ｍｌをトリーｎ−オクチルアルミニウム４．５ｍｌに、
テトラ−ｎ−へキシルチタネート２．４ｍｌをテトラ−
ｎ−オクチルチタネート３．０ｍｌに、クメンの量を２
．５ｍｌに、重合触媒量を５ｍｌにかえてアセチレンを
重合した。Example 2 Actual Mli Example 1 tri-n-hexylaluminum 3.5
ml to 4.5 ml of tri-n-octyl aluminum,
Add 2.4 ml of tetra-n-hexyl titanate to tetra-n-hexyl titanate.
Add 2 amounts of cumene to 3.0 ml of n-octyl titanate.
．． Acetylene was polymerized by changing the amount of polymerization catalyst to 5 ml.
実施例３
実施例１のトリーｎ−ヘキシルアルミニウム３．５ｍｌ
をトリーミーデシルアルミニウム５．５ｍｌに、テトラ
−ｎ−へキシルチタネート２．４ｍｌをテトラ−ｎ−オ
クチルチタネート３．０ｍｌに、クメンの量を５．５ｍ
ｌに、重合触媒量を７ｍｌにかえてアセチレンを重合し
た。Example 3 3.5 ml of tri-n-hexylaluminum from Example 1
to 5.5 ml of treated decyl aluminum, 2.4 ml of tetra-n-hexyl titanate to 3.0 ml of tetra-n-octyl titanate, and the amount of cumene to 5.5 ml.
Acetylene was polymerized by changing the amount of polymerization catalyst to 7 ml.
実施例４
実施例１のトリーｎ−ヘキシルアルミニウム３．５ｍｌ
をトリーｎ−デシルアルミニウム５．５ｍｌに、テトラ
−ｎ−へキシルチタネート２．４ｍｌをテトラ−ｎ−デ
シルチタネート３．４ｍｌに、り、メンの量を５．１ｍ
ｌに、重合触媒量を７ｍｌにかえてアセチレンを重合し
た。Example 4 3.5 ml of tri-n-hexylaluminum from Example 1
To 5.5 ml of tri-n-decyl aluminum and 2.4 ml of tetra-n-hexyl titanate to 3.4 ml of tetra-n-decyl titanate, the amount of aluminum was 5.1 ml.
Acetylene was polymerized by changing the amount of polymerization catalyst to 7 ml.
比較例１
実施例１のトリーローオクチルアルミニウム４．５ｍｌ
をトリエチルアルミニウム１．４ｍｌに、テトラ−ｎ−
へキシルチタネート２．４ｍｌをテトラ−ｎ−プチルチ
タネー）１．７ｍｌに、クメンの量を１．８ｍｌにかえ
てアセチレンを重合した。Comparative Example 1 4.5 ml of Trilow octyl aluminum of Example 1
to 1.4 ml of triethylaluminum, tetra-n-
Acetylene was polymerized by changing 2.4 ml of hexyl titanate to 1.7 ml of tetra-n-butyl titanate and changing the amount of cumene to 1.8 ml.
実施例１〜４および比較例のポリアセチレンの延伸率の
測定結果を表に示す。The measurement results of the stretching ratios of the polyacetylenes of Examples 1 to 4 and Comparative Examples are shown in the table.
表
表から明らかなように、比較例のトリエチルアルミニウ
ムーテトラ−ｎ−ブトキシチタネート系のチーグラー・
ナッタ触媒で重合したポリアセチレンの延伸率は４倍で
あったが、本発明のチーグラー・ナッタ触媒で重合した
ポリアセチレンの延伸率は８倍以上であった。ここでい
う延伸率とはそれ以上では伸びず、破断する限界（延伸
可能な倍率）を示す。As is clear from the table, the comparative example triethylaluminum-tetra-n-butoxytitanate Ziegler
The stretching ratio of the polyacetylene polymerized with the Natta catalyst was 4 times, but the stretching ratio of the polyacetylene polymerized with the Ziegler-Natta catalyst of the present invention was 8 times or more. The stretching ratio here indicates the limit (stretching ratio) beyond which the film will not stretch and will break.
また、本発明のポリアセチレンを延伸後、２Ｘ２０ｍｍ
に切取り、気相でヨウ素をドープしながら、四端子法で
延伸方向の導電率を測定したところ、１０”〜１０’Ｓ
／ｃｍの値を示した。In addition, after stretching the polyacetylene of the present invention, 2 x 20 mm
The electrical conductivity in the stretching direction was measured using the four-terminal method while doping with iodine in the vapor phase.
/cm values are shown.
発明の効果炸某
本発明によれば、アセチレンをトリアルキルアルミニウ
ムとテトラアルキルチタネートからなるチーグラー−ナ
ツタ触媒により重合する方法において、前記トリアルキ
ルアルミニウムおよび前記テトラアルキルチタネートが
両方とも炭素数８以上のアルキル基を持つチーグラー−
ナツタ触媒を用いることにより、延伸性の優れたポリア
セチレンが得られる。According to the present invention, in a method for polymerizing acetylene using a Ziegler-Natsuta catalyst consisting of an aluminum trialkyl and a tetraalkyl titanate, both the aluminum trialkyl and the tetraalkyl titanate are alkyl groups having 8 or more carbon atoms. Ziegler with base
By using Natsuta's catalyst, polyacetylene with excellent stretchability can be obtained.
Claims (2)
アルキルチタネートからなるチーグラー・ナッタ触媒に
より重合する方法において、前記トリアルキルアルミニ
ウムおよび前記テトラアルキルチタネートが両方とも長
鎖のアルキル基を持つことを特徴とするポリアセチレン
の製造法。(1) A method of polymerizing acetylene using a Ziegler-Natta catalyst consisting of a trialkylaluminum and a tetraalkyl titanate, wherein the trialkylaluminum and the tetraalkyl titanate both have long-chain alkyl groups. Manufacturing method.
ある請求項１記載のポリアセチレンの製造法。(2) The method for producing polyacetylene according to claim 1, wherein the long-chain alkyl group is an alkyl group having 6 or more carbon atoms.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9017589A JPH0651759B2 (en) | 1989-04-10 | 1989-04-10 | Method for producing polyacetylene |
| US07/465,421 US4983696A (en) | 1989-01-25 | 1990-01-16 | Process for producing polyacetylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9017589A JPH0651759B2 (en) | 1989-04-10 | 1989-04-10 | Method for producing polyacetylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02269107A true JPH02269107A (en) | 1990-11-02 |
| JPH0651759B2 JPH0651759B2 (en) | 1994-07-06 |
Family
ID=13991152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9017589A Expired - Lifetime JPH0651759B2 (en) | 1989-01-25 | 1989-04-10 | Method for producing polyacetylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0651759B2 (en) |
-
1989
- 1989-04-10 JP JP9017589A patent/JPH0651759B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0651759B2 (en) | 1994-07-06 |
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