JPH0967429A - New phenylene polymer, its production and organic conductive material using the polymer - Google Patents
New phenylene polymer, its production and organic conductive material using the polymerInfo
- Publication number
- JPH0967429A JPH0967429A JP24511995A JP24511995A JPH0967429A JP H0967429 A JPH0967429 A JP H0967429A JP 24511995 A JP24511995 A JP 24511995A JP 24511995 A JP24511995 A JP 24511995A JP H0967429 A JPH0967429 A JP H0967429A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- formula
- conductive material
- poly
- organic conductive
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 239000004020 conductor Substances 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 title description 3
- -1 poly(benzonitrile) Polymers 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052786 argon Inorganic materials 0.000 abstract description 4
- 150000003003 phosphines Chemical class 0.000 abstract description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 33
- 238000006722 reduction reaction Methods 0.000 description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LNGWRTKJZCBXGT-UHFFFAOYSA-N 2,5-dichlorobenzonitrile Chemical compound ClC1=CC=C(Cl)C(C#N)=C1 LNGWRTKJZCBXGT-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000008359 benzonitriles Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規なフェニレン系
重合体、その製造方法及びそれを用いた有機導電材料に
関するものである。TECHNICAL FIELD The present invention relates to a novel phenylene polymer, a method for producing the same, and an organic conductive material using the same.
【０００２】[0002]
【従来の技術】従来、ポリ（ｐ−フェニレン）がベンゼ
ンの電解酸化重合あるいはジハロゲン化ベンゼン類の電
解還元重合によって製造されることが知られており（Ch
em. Lett., 457(1992); Polymer, 34,401(1993)）、得
られたポリマーの酸化あるいは還元により陰イオンある
いは陽イオンがドーピングされｐ型あるいはｎ型半導体
となる。この性質を利用してポリ（ｐ−フェニレン）の
電極材料への応用及び酸化・還元時の吸光度変化を用い
た表示素子としての応用が可能である。しかしながら還
元によってｎ型半導体とするためには、−２Ｖ以下の電
位を印加する必要があるので、溶媒もしくは支持電解質
の分解を招きやすいという欠点があり、実用化されるに
至っていない。2. Description of the Related Art It has been known that poly (p-phenylene) is produced by electrolytic oxidation polymerization of benzene or electrolytic reduction polymerization of dihalogenated benzenes (Ch).
Em. Lett., 457 (1992); Polymer, 34 , 401 (1993)), and anion or cation is doped by oxidation or reduction of the obtained polymer to be a p-type or n-type semiconductor. Utilizing this property, it is possible to apply poly (p-phenylene) as an electrode material and as a display element using the change in absorbance during oxidation / reduction. However, in order to form an n-type semiconductor by reduction, it is necessary to apply a potential of −2 V or less, and therefore, there is a disadvantage that the solvent or the supporting electrolyte is easily decomposed, and thus has not been put to practical use.
【０００３】[0003]
【発明が解決しようとする課題】本発明者らは、このよ
うな欠点を克服すべく鋭意研究を行った結果、ある種の
ポリ（ｐ−フェニレン）誘導体がその目的に適合するこ
とを見い出し、本発明を完成するに至ったもので、本発
明の目的は−２Ｖ以上の溶媒及び支持電解質の分解が起
こりにくい穏和な条件下で還元反応が可能な有機導電材
料及びその製造技術を提供することである。The present inventors have made intensive studies to overcome such drawbacks, and as a result, have found that certain poly (p-phenylene) derivatives are suitable for the purpose. The present invention has been completed, and an object of the present invention is to provide an organic conductive material capable of a reduction reaction under mild conditions in which decomposition of a solvent and a supporting electrolyte of −2 V or more does not easily occur, and a production technique thereof. It is.
【０００４】[0004]
【課題を解決するための手段】すなわち、本発明は式
（Ｉ）That is, the present invention provides formula (I)
【０００５】[0005]
【化５】 Embedded image
【０００６】で示される繰り返し単位からなる重合体で
あり、この製法として式（II）A polymer comprising a repeating unit represented by the formula (II)
【０００７】[0007]
【化６】 [Chemical 6]
【０００８】（式中のＸはＣｌ、ＢｒもしくはＩを示
す。）で示される化合物をハロゲン化ニッケルの存在下
で重縮合させることを特徴とする、式（Ｉ）Wherein X represents Cl, Br or I. The compound represented by formula (I) is polycondensed in the presence of nickel halide.
【０００９】[0009]
【化７】 [Chemical 7]
【００１０】で示される繰り返し単位からなる重合体の
製造方法であって、更に、得られた式（Ｉ）A process for producing a polymer comprising a repeating unit represented by the formula (I)
【００１１】[0011]
【化８】 Embedded image
【００１２】で示される繰り返し単位からなる重合体に
陽イオンをドーピングさせて成る有機導電材料である。It is an organic conductive material obtained by doping a polymer having a repeating unit represented by the formula with a cation.
【００１３】式（Ｉ）Formula (I)
【化９】 Embedded image
【００１４】で示される繰り返し単位から成るポリ（ベ
ンゾニトリル）は新規化合物であって、Ｎ，Ｎ−ジメチ
ルホルムアミド、ジメチルスルホキシドなどの溶媒に可
溶なので、フィルムなどに成形することができる。Poly (benzonitrile) comprising a repeating unit represented by the formula (1) is a novel compound and is soluble in solvents such as N, N-dimethylformamide and dimethylsulfoxide, and can be formed into a film or the like.
【００１５】[0015]
【発明の実施の形態】このポリ（ベンゾニトリル）は式
（II）DETAILED DESCRIPTION OF THE INVENTION The poly (benzonitrile) has the formula (II)
【００１６】[0016]
【化１０】 Embedded image
【００１７】（式中のＸはＣｌ、ＢｒもしくはＩを示
す。）で示されるジハロゲン化ベンゾニトリルをハロゲ
ン化ニッケル、置換ホスフィン及び亜鉛を用いて重縮合
することにより製造することができる。置換ホスフィン
としては、トリフェニルホスフィンなどのトリアリール
ホスフィン又はトリエチルホスフィン、トリイソプロピ
ルホスフィン等のトリアルキルホスフィンが用いられる
がトリフェニルホスフィンが好ましい。この際に用いら
れるハロゲン化ニッケルとしては、塩化ニッケル、臭化
ニッケルなどがあげられ、また、亜鉛の代わりにマンガ
ン、マグネシウムなどを用いることができる。反応溶媒
としてはＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメ
チルアセトアミドなどが適しており、加熱温度としては
４０〜１２０℃、好ましくは５０〜８０℃の範囲であ
る。重合は反応中間体が酸素と化合して副生物を生じる
のを防ぐため、不活性雰囲気下で行う。この際の不活性
雰囲気としては窒素、アルゴンなどが用いられる。(Wherein X in the formula represents Cl, Br or I). It can be produced by polycondensation of a dihalogenated benzonitrile using a nickel halide, a substituted phosphine and zinc. As the substituted phosphine, a triarylphosphine such as triphenylphosphine or a trialkylphosphine such as triethylphosphine or triisopropylphosphine is used, and triphenylphosphine is preferable. Examples of the nickel halide used at this time include nickel chloride and nickel bromide, and manganese and magnesium can be used instead of zinc. N, N-dimethylformamide, N, N-dimethylacetamide and the like are suitable as the reaction solvent, and the heating temperature is 40 to 120 ° C, preferably 50 to 80 ° C. The polymerization is carried out under an inert atmosphere to prevent the reaction intermediate from combining with oxygen to produce a by-product. Nitrogen, argon, etc. are used as the inert atmosphere at this time.
【００１８】ハロゲン化ニッケルは亜鉛などの還元性金
属によりゼロ価ニッケルになり、ジハロゲン化ベンゾニ
トリルと錯体を作り、この錯体がもう一つのジハロゲン
化ベンゾニトリルと付加する過程を経て、ベンゾニトリ
ルが２量化する。以下、この経路を繰り返すことにより
ポリ（ベンゾニトリル）が生成するものと考えられる。
ハロゲン化ニッケルの使用量は特に制限はないが、式
（II）で表わされる化合物に対し、 2モル％以上、好ま
しくは 5〜20モル％である。置換ホスフィンの使用量は
特に制限はないが式（II）で表わされる化合物に対し、
10モル％以上、好ましくは20〜80モル％であり、亜鉛、
マンガン、マグネシウムの使用量も特に制限はないが式
（II）で表わされる化合物に対し、モル比で 0.5倍以
上、好ましくは 1〜 5倍である。The nickel halide is converted to zero-valent nickel by a reducing metal such as zinc, and forms a complex with the dihalogenated benzonitrile. Quantify. Hereinafter, it is considered that poly (benzonitrile) is generated by repeating this route.
The amount of nickel halide used is not particularly limited, but is at least 2 mol%, preferably 5 to 20 mol%, based on the compound represented by the formula (II). The amount of the substituted phosphine used is not particularly limited, but is based on the compound represented by the formula (II).
10 mol% or more, preferably 20 to 80 mol%, zinc,
The use amount of manganese and magnesium is not particularly limited, either, but it is 0.5 times or more, preferably 1 to 5 times in molar ratio to the compound represented by the formula (II).
【００１９】本発明の式（Ｉ）で示される繰り返し単位
からなる重合体はその中に赤外吸収スペクトルで検知し
うるＣ＝Ｏ結合を有しないという特徴を有する。その分
子量は、通常 500〜10000 、好ましくは1000〜10000 で
ある。従来法ではフェニレン系重合体の製造には電解還
元重合を用いている。この方法は電位の大きさによって
反応を進行させようとするものであり、例えば原料の
２，５−ジクロロベンゾニトリルが容易には還元され
ず、−２．５Ｖという負の大きな電位が必要となるた
め、重合中間体がきわめて不安定なものとなり、簡単に
酸化されこれがＣ＝Ｏの生成として現れるものと考えら
れる。これに対し、本発明の方法では、錯体の生成によ
り穏和な条件で還元反応が進行し、このような酸化物が
認められない。本発明の方法により得られたポリ（ベン
ゾニトリル）はそのままの状態では絶縁体であるが、テ
トラメチルアンモニウムイオン、テトラエチルアンモニ
ウムイオン、テトラ−ｎ−ブチルアンモニウムイオン、
リチウムイオン、ナトリウムイオン、カリウムイオンな
どの陽イオンをドーピングすることにより半導体として
の性質を示すようになる。ドーピングする陽イオンの量
は式（Ｉ）で示される繰り返し単位からなる重合体に対
し、繰り返し単位当り 1モル％以上、好ましくは 5〜50
モル％である。このドーピングは電極上に作ったポリ
（ベンゾニトリル）膜に、支持電解質を溶解した溶媒中
で電位を印加することにより行うことができる。The polymer of the present invention comprising a repeating unit represented by the formula (I) is characterized in that it has no C ＝ O bond detectable in the infrared absorption spectrum. Its molecular weight is usually from 500 to 10,000, preferably from 1,000 to 10,000. In the conventional method, electrolytic reduction polymerization is used for producing a phenylene-based polymer. In this method, the reaction is advanced according to the magnitude of the potential. For example, the starting material 2,5-dichlorobenzonitrile is not easily reduced, and a large negative potential of -2.5 V is required. Therefore, it is considered that the polymerization intermediate becomes extremely unstable and is easily oxidized, and this appears as formation of CＣO. On the other hand, in the method of the present invention, the reduction reaction proceeds under mild conditions due to the formation of the complex, and no such oxide is observed. The poly (benzonitrile) obtained by the method of the present invention is an insulator as it is, but it has tetramethylammonium ion, tetraethylammonium ion, tetra-n-butylammonium ion,
By doping with cations such as lithium ions, sodium ions, and potassium ions, semiconductor properties are exhibited. The amount of the cation to be doped is 1 mol% or more, preferably 5 to 50 mol%, per the repeating unit represented by the formula (I).
Mol%. This doping can be performed by applying a potential to a poly (benzonitrile) film formed on the electrode in a solvent in which a supporting electrolyte is dissolved.
【００２０】[0020]
【発明の効果】本発明によれば、溶媒に可溶で容易に成
形しうるポリ（ベンゾニトリル）を製造することがで
き、また、このポリマーは−２Ｖ以上の穏和な条件下で
の還元反応が可能である。According to the present invention, poly (benzonitrile) which is soluble in a solvent and can be easily molded can be produced, and this polymer can be subjected to a reduction reaction under mild conditions of -2 V or more. Is possible.
【００２１】[0021]
【実施例】次に、実施例により本発明を更に詳細に説明
する。Next, the present invention will be described in more detail by way of examples.
【００２２】実施例１ 還流冷却器、マグネチックスターラー付き30ml三頚フラ
スコに、塩化ニッケル0.065g(0.50 ミリモル) 、トリフ
ェニルホスフィン1.0g(3.8ミリモル) 及び亜鉛1.0g(15.
3 ミリモル) を入れ、系を真空にした後に窒素ガスを導
入するという操作を３回繰り返して不活性雰囲気とし
た。乾燥したＮ，Ｎ−ジメチルホルムアミド４mlをセプ
タムキャップから注射器によって加え、80℃に昇温する
と赤褐色を呈した。２，５−ジクロロベンゾントリル
0.86g(5.0ミリモル) を乾燥Ｎ，Ｎ−ジメチルホルムア
ミド５mlに溶解し窒素置換したものを加えると、緑色に
変化した後に次第に赤褐色となった。18時間かくはん
し、反応混合物をエーテル300mlに入れ、過剰の亜鉛及
び未反応モノマーを除去し、１Ｎ塩酸100ml で２回処理
後、水、メタノールで洗浄し、真空乾燥を行った。黄白
色粉末0.267g(53%) を得た。融点378 〜384 ℃（一部分
解）。このポリ（ベンゾニトリル）の赤外吸収スペクト
ルを図１に示す。これより、 833，2223cm-1 にバンド
が観測され、それぞれ１，２，４−トリ置換ベンゼンの
面外変角振動、Ｃ≡Ｎ結合の伸縮振動に帰属される。Example 1 In a 30 ml three-necked flask equipped with a reflux condenser and a magnetic stirrer, 0.065 g (0.50 mmol) of nickel chloride, 1.0 g (3.8 mmol) of triphenylphosphine and 1.0 g (15.
(3 mmol) was added, the system was evacuated, and then nitrogen gas was introduced, which was repeated three times to create an inert atmosphere. 4 ml of dried N, N-dimethylformamide was added by a syringe from a septum cap, and when the temperature was raised to 80 ° C., it turned reddish brown. 2,5-dichlorobenzonthril
When 0.86 g (5.0 mmol) was dissolved in 5 ml of dry N, N-dimethylformamide and the mixture was replaced with nitrogen, the mixture turned green and then gradually became reddish brown. After stirring for 18 hours, the reaction mixture was poured into 300 ml of ether to remove excess zinc and unreacted monomers, treated twice with 100 ml of 1N hydrochloric acid, washed with water and methanol, and dried in vacuo. 0.267 g (53%) of a yellowish white powder was obtained. 378-384 ° C (partially decomposed). FIG. 1 shows the infrared absorption spectrum of this poly (benzonitrile). From this, a band was observed at 833,2223 cm −1 , which was attributed to the out-of-plane bending vibration of 1,2,4-trisubstituted benzene and the stretching vibration of the C≡N bond, respectively.
【００２３】実施例２ 実施例１における仕込量を塩化ニッケル0.033g(0.25 ミ
リモル) 、トリフェニルホスフィン0.5g(1.9ミリモル)
及び亜鉛0.5g(7.65 ミリモル) としたほかは同様に操作
を行った。淡黄色粉末0.218g(43%) を得た。融点386 〜
393 ℃（一部分解）。Example 2 In Example 1, the charged amounts were 0.033 g (0.25 mmol) of nickel chloride and 0.5 g (1.9 mmol) of triphenylphosphine.
And 0.5 g (7.65 mmol) of zinc. 0.218 g (43%) of a pale yellow powder was obtained. Melting point 386 ~
393 ° C (partially decomposed).
【００２４】実施例３ 実施例１における仕込量を塩化ニッケル0.0165g(0.125
ミリモル) 、トリフェニルホスフィン0.25g(0.95ミリモ
ル) 及び亜鉛0.25g(3.83ミリモル) としたほかは同様に
操作を行った。灰白色粉末0.015g(3%)を得た。融点361
〜372 ℃（一部分解）。Example 3 The charge in Example 1 was changed to 0.0165 g (0.125 g) of nickel chloride.
Mmol), 0.25 g (0.95 mmol) of triphenylphosphine and 0.25 g (3.83 mmol) of zinc. 0.015 g (3%) of an off-white powder was obtained. Melting point 361
~ 372 ° C (partially decomposed).
【００２５】実施例４ 実施例１で得られたポリ（ベンゾニトリル）を、Ｎ，Ｎ
−ジメチルホルムアミドに溶解し、白金板上に塗布、乾
燥させてフィルムを作成した。この白金板を作用電極、
銀線を参照電極として、炭酸プロピレン中、0.1 Ｍ テ
トラフルオロホウ酸テトラ−ｎ−ブチルアンモニウムを
支持電解質として、100 ｍＶ／Ｓの掃引速度で0 〜−2.
1 Ｖ（vs Ag)の範囲でサイクリックボルタモグラムを測
定すると、−1.65Ｖにポリマーが中性状態からｎ型半導
体への変化を表す還元ピークが認められた。この還元電
位は溶媒を炭酸プロピレンからテトラヒドロフランに代
えると、-1.3Ｖ（vs Ag)となった。Example 4 The poly (benzonitrile) obtained in Example 1 was converted to N, N
-Dissolved in dimethylformamide, applied on a platinum plate and dried to form a film. This platinum plate is used as a working electrode,
Using a silver wire as a reference electrode and 0.1 M tetra-n-butylammonium tetrafluoroborate in propylene carbonate as a supporting electrolyte at a sweep rate of 100 mV / S to 0--2.
When a cyclic voltammogram was measured in the range of 1 V (vs Ag), a reduction peak indicating a change of the polymer from a neutral state to an n-type semiconductor was observed at -1.65 V. The reduction potential was -1.3 V (vs Ag) when the solvent was changed from propylene carbonate to tetrahydrofuran.
【００２６】比較例 作用電極及び対極として白金板、参照電極として銀線を
備えたアルゴンガス導入管付き20ml四頸フラスコに乾燥
したテトラヒドロフラン15mlを入れ、２，５−ジクロロ
ベンゾニトリル0.129g（0.75ミリモル）、テトラフルオ
ロホウ酸テトラ−ｎ−ブチルアンモニウム0.494g(1.5ミ
リモル）を加えて溶解させた後、アルゴンガスを導入
し、不活性雰囲気とした。作用電極に-2.5Ｖの電位を印
加し６時間通電すると黄褐色のフィルムが得られた。こ
のようにして得られたポリ（ベンゾニトリル）の赤外吸
収スペクトルは1720cm-1に、Ｃ＝Ｏ結合の存在を示す吸
収がみられた。このポリ（ベンゾニトリル）を使って実
施例４と同様にドーピングを行ってテトラヒドロフラン
中での還元電位を測定したところ、-2.1Ｖ（vs Ag)であ
った。COMPARATIVE EXAMPLE 15 ml of dried tetrahydrofuran was placed in a 20 ml four-necked flask equipped with a platinum plate as a working electrode and a counter electrode and a silver wire as a reference electrode and provided with an argon gas inlet tube, and 0.129 g (0.75 mmol) of 2,5-dichlorobenzonitrile ) And 0.494 g (1.5 mmol) of tetra-n-butylammonium tetrafluoroborate were added and dissolved, and then an inert gas was introduced by introducing argon gas. When a potential of -2.5 V was applied to the working electrode and energized for 6 hours, a yellow-brown film was obtained. The infrared absorption spectrum of the poly (benzonitrile) thus obtained showed an absorption at 1720 cm -1 indicating the presence of a C ＝ O bond. Doping was carried out in the same manner as in Example 4 using this poly (benzonitrile), and the reduction potential in tetrahydrofuran was measured to be -2.1 V (vs Ag).
【図１】ポリ（ベンゾニトリル）の赤外吸収スペクトル
図である。FIG. 1 is an infrared absorption spectrum of poly (benzonitrile).
Claims (3)
る化合物をハロゲン化ニッケルの存在下で重縮合させる
ことを特徴とする、式（Ｉ） 【化３】 で示される繰り返し単位から成る重合体の製造方法。2. Formula (II): Wherein X represents Cl, Br or I. The compound represented by the formula (I) is polycondensed in the presence of nickel halide. A method for producing a polymer comprising a repeating unit represented by:
ーピングさせて成る有機導電材料。3. Formula (I): An organic conductive material obtained by doping a polymer having a repeating unit represented by the formula with a cation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7245119A JP2816426B2 (en) | 1995-08-31 | 1995-08-31 | Novel phenylene polymer, method for producing the same, and organic conductive material using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7245119A JP2816426B2 (en) | 1995-08-31 | 1995-08-31 | Novel phenylene polymer, method for producing the same, and organic conductive material using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0967429A true JPH0967429A (en) | 1997-03-11 |
| JP2816426B2 JP2816426B2 (en) | 1998-10-27 |
Family
ID=17128910
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7245119A Expired - Lifetime JP2816426B2 (en) | 1995-08-31 | 1995-08-31 | Novel phenylene polymer, method for producing the same, and organic conductive material using the same |
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| Country | Link |
|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005206826A (en) * | 2003-12-25 | 2005-08-04 | Sumitomo Chemical Co Ltd | Method for producing polymer compound |
| JP2012214689A (en) * | 2011-03-28 | 2012-11-08 | Sumitomo Chemical Co Ltd | Composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5643318A (en) * | 1979-09-11 | 1981-04-22 | Union Carbide Corp | Coupling of arylpolyhalide and heteroarylpolyhalide |
-
1995
- 1995-08-31 JP JP7245119A patent/JP2816426B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5643318A (en) * | 1979-09-11 | 1981-04-22 | Union Carbide Corp | Coupling of arylpolyhalide and heteroarylpolyhalide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005206826A (en) * | 2003-12-25 | 2005-08-04 | Sumitomo Chemical Co Ltd | Method for producing polymer compound |
| JP2012214689A (en) * | 2011-03-28 | 2012-11-08 | Sumitomo Chemical Co Ltd | Composition |
| US9601696B2 (en) | 2011-03-28 | 2017-03-21 | Sumitomo Chemical Company, Limited | Electroluminescent composition and electric device with high brightness |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2816426B2 (en) | 1998-10-27 |
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