JPH0520454B2 - - Google Patents
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- Publication number
- JPH0520454B2 JPH0520454B2 JP20972986A JP20972986A JPH0520454B2 JP H0520454 B2 JPH0520454 B2 JP H0520454B2 JP 20972986 A JP20972986 A JP 20972986A JP 20972986 A JP20972986 A JP 20972986A JP H0520454 B2 JPH0520454 B2 JP H0520454B2
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- Japan
- Prior art keywords
- polymer
- formula
- reaction
- alkyl group
- carbon atoms
- Prior art date
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- 229920000642 polymer Polymers 0.000 claims description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- -1 Paraphenylene Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001746 electroactive polymer Polymers 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 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 2
- 238000005406 washing Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 1
- BIRGXTCAZOKDQE-UHFFFAOYSA-N 3,4-dichloro-2-pyridin-2-ylpyridine Chemical compound ClC1=CC=NC(C=2N=CC=CC=2)=C1Cl BIRGXTCAZOKDQE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SRENRFDRXNVMKN-UHFFFAOYSA-N n-butyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCC)C1=CC=CC=C1 SRENRFDRXNVMKN-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- QEKXARSPUFVXIX-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dibromide Chemical compound [Ni+2].[Br-].[Br-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QEKXARSPUFVXIX-UHFFFAOYSA-L 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Description
【発明の詳細な説明】
＜産業上の利用分野＞
本発明は、導電性高分子に利用可能な次式
（）で表わされる４，4′−ジフエニルアミン構
造を繰り返し単位とする重合体の製造方法に関す
る。Detailed Description of the Invention <Industrial Application Field> The present invention provides a method for producing a polymer having a 4,4'-diphenylamine structure as a repeating unit, which can be used as a conductive polymer and is represented by the following formula (). Regarding.
（式中、Ｒは炭素数１〜６のアルキル基を示す）
＜従来の技術及び発明が解決しようとする問題点
＞
導電性高分子材料を形成するのに用いられる重
合体として、ポリアセチレン、ポリパラフエニレ
ン、ポリチオフエン、ポリピロール等が知られて
いる。これ等の重合体は、ある種の化合物をドー
プすることにより導電性高分子材料として使用可
能となるが、空気中で変質しやすく、電気的特性
が変化する。また融解性、溶解性等に乏しく加工
性が極めて悪い等の問題点があり、実用上の大き
な障害となつている。 (In the formula, R represents an alkyl group having 1 to 6 carbon atoms.) <Prior art and problems to be solved by the invention> As polymers used to form the conductive polymer material, polyacetylene, polyester, Paraphenylene, polythiophene, polypyrrole, etc. are known. These polymers can be used as conductive polymer materials by doping them with certain compounds, but they are easily degraded in the air and their electrical properties change. In addition, there are problems such as poor meltability and solubility, and extremely poor processability, which is a major obstacle in practical use.
これらの問題を解決する方法として特開昭59−
102928号では、各種のヘテロジアゾール系の電気
活性ポリマーが提案されており、たとえば下記の
ような一般式で表わされるポリオキサジアゾール
系ポリマーが有効であることが示されている。 As a way to solve these problems,
No. 102928 proposes various heterodiazole-based electroactive polymers, and for example, polyoxadiazole-based polymers represented by the following general formula have been shown to be effective.
しかしながら、上記のポリマーは合成法が複雑
であるうえ、生成したポリマーの吸湿性が大き
く、又化学的な安定性に乏しいなど問題点が多
い。 However, the above-mentioned polymers have many problems such as complicated synthesis methods, high hygroscopicity of the produced polymers, and poor chemical stability.
また、特開昭61−28524号では、各種のトリフ
エニルアミン系の電気活性ポリマーが提案されて
おり、たとえば下記のような一般式で表わされる
トリフエニルアミン系ポリマーが有効であること
が示されている。 Furthermore, in JP-A No. 61-28524, various triphenylamine-based electroactive polymers have been proposed, and for example, triphenylamine-based polymers represented by the following general formula have been shown to be effective. ing.
しかし、上記トリフエニルアミン系ポリマーに
おいては、その出発原料であるトリフエニルアミ
ンおよびそのジハロゲン化物である、４，4′−ジ
ハロトリフエニルアミンの合成は困難であり、か
つジハロゲン化物を選択性良く得ることができな
いという欠点があるばかりか、直鎖状の重合体が
得られにくいという欠点もある。 However, in the above-mentioned triphenylamine-based polymer, it is difficult to synthesize triphenylamine, which is the starting material, and 4,4'-dihalotriphenylamine, which is its dihalide, and it is difficult to synthesize the dihalide with good selectivity. Not only does it have the disadvantage that it cannot be obtained, but it also has the disadvantage that it is difficult to obtain a linear polymer.
＜問題点を解決するための手段＞
本発明によれば、下記一般式（）
（式中、Ｒは炭素数１〜６のアルキル基を示し、
Ｘはハロゲンを示す）で表わされる４，4′−ジハ
ロフエニルに、金属マグネシウムを作用させ、次
いでニツケル化合物を触媒として重合することを
特徴とする下記一般式（）で表わされる４，
4′−ジフエニルアミン構造を繰り返し単位とする
重合体の製造方法
（式中、Ｒは炭素数１〜６のアルキル基を示す）
が提供される。<Means for solving the problems> According to the present invention, the following general formula () (In the formula, R represents an alkyl group having 1 to 6 carbon atoms,
4,4'-dihalophenyl (X represents halogen) is reacted with metallic magnesium and then polymerized using a nickel compound as a catalyst.
Method for producing a polymer having a 4'-diphenylamine structure as a repeating unit (wherein R represents an alkyl group having 1 to 6 carbon atoms) is provided.
本発明の製造方法では、下記（）式で示され
る、４，4′−ジハロジフエニル（式中、Ｒは炭素
数１〜６のアルキル基を示し、Ｘはハロゲンを示
す。）に金属マグネシウムを作用させ、下記（）
式で示される化合物を得、次いで化合物（）を
ニツケル化合物を触媒として重合させることによ
り、前記一般式（）で表わされる４，4′−ジフ
エニルアミン構造を繰り返し単位とする重合体を
得ることができる。 In the production method of the present invention, metallic magnesium is applied to 4,4'-dihalodiphenyl (in the formula, R represents an alkyl group having 1 to 6 carbon atoms and X represents a halogen) represented by the following formula (). Let the following ()
By obtaining a compound represented by the formula and then polymerizing the compound () using a nickel compound as a catalyst, a polymer having a 4,4'-diphenylamine structure represented by the general formula () as a repeating unit can be obtained. .
反応は、非反応性溶媒中で行うのが望ましい。 Preferably, the reaction is carried out in a non-reactive solvent.
反応温度は、−20℃〜200℃、好ましくは、０〜
150℃の範囲で選ぶことができる。 The reaction temperature is -20°C to 200°C, preferably 0 to 200°C.
You can choose from a range of 150℃.
また、本発明の重合体は下記の方法によつても
得ることができる。 Moreover, the polymer of the present invention can also be obtained by the following method.
上記反応に用いられる非反応性溶媒としては、
ジエチルエーテル、テトラヒドロフラン、ジブチ
ルエーテルなどがある。 The non-reactive solvent used in the above reaction is
Examples include diethyl ether, tetrahydrofuran, and dibutyl ether.
また、触媒として用いるニツケル化合物として
は、ジクロロニツケル、ジブロモニツケル、ジク
ロロ（２，2′−ビピリジン）ニツケル、ジブロモ
ビス（トリフエニルホスフイン）ニツケル、１，
５−シクロオクタジエンビス（トリフエニルホス
フイン）ニツケルのようなニツケル化合物が用い
られる。 In addition, the nickel compounds used as catalysts include dichloronickel, dibromonnickel, dichloro(2,2'-bipyridine)nickel, dibromobis(triphenylphosphine)nickel, 1,
Nickel compounds such as 5-cyclooctadienebis(triphenylphosphine)nickel are used.
なお、本発明の重合体を合成する方法として、
酸化重合法、電解重合法も好ましく用いることが
できる。 In addition, as a method for synthesizing the polymer of the present invention,
Oxidative polymerization methods and electrolytic polymerization methods can also be preferably used.
本発明の重合体は、実質的に線状であるため、
加工性にすぐれており、熱可塑性高分子として各
種の成形体とすることができる。 Since the polymer of the present invention is substantially linear,
It has excellent processability and can be made into various molded products as a thermoplastic polymer.
また、ニトロベンゼン、２，４−ジニトロクロ
ロベンゼンおよび２，４−ジニトロフルオロベン
ゼンのような電子受容性の有機溶媒や、硫酸、蟻
酸、ポリリン酸等の強酸溶媒中に溶解させて、フ
イルム、シートなどに成形することもできる。 It can also be dissolved in electron-accepting organic solvents such as nitrobenzene, 2,4-dinitrochlorobenzene, and 2,4-dinitrofluorobenzene, or in strong acid solvents such as sulfuric acid, formic acid, and polyphosphoric acid to form films, sheets, etc. It can also be molded.
＜発明の効果＞
本発明の製造方法により得られる重合体は線状
であるため、加工性に優れており、容易に各種成
形体に製造することができる。<Effects of the Invention> Since the polymer obtained by the production method of the present invention is linear, it has excellent processability and can be easily produced into various molded products.
＜実施例＞
以下、本発明を実施例および参考例により具体
的に説明するが、本発明はこれらに限定されるも
のではない。<Examples> The present invention will be specifically explained below using Examples and Reference Examples, but the present invention is not limited thereto.
実施例 １
金属カリウム4.613ｇ（0.1180グラム原子量）、
ヨウ化カリウム（KI）9.79ｇ（0.0590モル）、塩
化マグネシウム（無水）5.62ｇ（0.0590モル）お
よび乾燥テトラヒドロフラン（THF）100mlを
300mlのフラスコ中、窒素雰囲気下でかきまぜな
がら加熱還流し、反応させた。約１時間後、黒色
の粉末を生じ、金属マグネシウムが生成したこと
を認めた。ついで、４，4′−ジブロモ−Ｎ−メチ
ルジフエニルアミン10.06ｇ（0.0295モル）を乾
燥THF50mlに溶解し、滴下漏斗から添加した。
添加終了後、１時間かきまぜながら、加熱還流し
た。更に、４，4′−ジブロモ−Ｎ−メチルジフエ
ニルアミン10.06ｇ（0.0295モル）とNiBr2
（Pph3）2（ph：フエニル）約0.03ｇを乾燥THF50
mlに溶解し、滴下漏斗で添加した。攪拌下加熱還
流を１日行つた後、生成物を塩酸酸性エタノール
中に注ぎ、１時間かきまぜた後、濾別した。フイ
ルター上で十分にエタノールで洗浄した後、ソツ
クスレー抽出器を用い、エタノールで１晩抽出
し、不純物を除去した。生成した重合体の乾燥後
の収量は8.55ｇであつた。Example 1 4.613 g (0.1180 gram atomic weight) of metallic potassium,
9.79 g (0.0590 mol) of potassium iodide (KI), 5.62 g (0.0590 mol) of magnesium chloride (anhydrous) and 100 ml of dry tetrahydrofuran (THF).
In a 300 ml flask, the mixture was heated to reflux while stirring under a nitrogen atmosphere to cause a reaction. After about 1 hour, black powder was produced, and it was recognized that metallic magnesium had been produced. 10.06 g (0.0295 mol) of 4,4'-dibromo-N-methyldiphenylamine was then dissolved in 50 ml of dry THF and added through the addition funnel.
After the addition was completed, the mixture was heated to reflux while stirring for 1 hour. Furthermore, 10.06 g (0.0295 mol) of 4,4'-dibromo-N-methyldiphenylamine and NiBr 2
(Pph 3 ) 2 (ph: phenyl) approximately 0.03g dried THF50
ml and added via addition funnel. After heating and refluxing for 1 day with stirring, the product was poured into ethanol acidified with hydrochloric acid, stirred for 1 hour, and then filtered. After thoroughly washing the filter with ethanol, the filter was extracted with ethanol overnight using a Soxhlet extractor to remove impurities. The yield of the resulting polymer after drying was 8.55 g.
かようにして得た重合体は薄緑色の粉末で、空
気中で３ケ月間放置しても何の変化もみられず、
きわめて安定であつた。また、この重合体の熱重
量分析を窒素雰囲気中で行つた。その結果を第１
図に示す。この図から重合体は350℃まで減量す
ることなく安定であり、700℃の高温でも約70％
の残存重量を示していることがわかる。 The polymer thus obtained was a light green powder, and no change was observed even after it was left in the air for three months.
It was extremely stable. Further, thermogravimetric analysis of this polymer was conducted in a nitrogen atmosphere. The result is the first
As shown in the figure. From this figure, the polymer is stable without weight loss up to 350℃, and even at a high temperature of 700℃, it is about 70%
It can be seen that the remaining weight of
また、元素分析をしたところ次の結果が得られ
た。 In addition, elemental analysis yielded the following results.
重合体の元素分析値：
炭素(C)84.17％ 水素(H)5.86％
窒素(N)7.67％
原子比はＣ：Ｈ：Ｎ＝12.8：10.7：１で理論値
（C13H11N）に近い値であつた。Elemental analysis values of the polymer: Carbon (C) 84.17% Hydrogen (H) 5.86% Nitrogen (N) 7.67% The atomic ratio is C:H:N=12.8:10.7:1, which is the theoretical value (C 13 H 11 N) The values were close.
次に重合体の赤外スペクトル分析を行い、測定
した赤外スペクトルを第２図に示す。図中1590cm
-1、1490cm-1および1320cm-1付近の吸収はジフエ
ニルアミン構造によるものであり、800cm-1付近
の吸収はパラ置換ベンゼン構造によるものであ
る。 Next, the polymer was subjected to infrared spectrum analysis, and the measured infrared spectrum is shown in FIG. 1590cm in the figure
-1 , 1490 cm -1 and 1320 cm -1 are due to the diphenylamine structure, and absorption near 800 cm -1 is due to the para-substituted benzene structure.
これ等の結果より生成重合体がポリ（４，4′−
Ｎ−メチル−ジフエニルアミン）であることが確
認できた。 These results show that the produced polymer is poly(4,4'-
N-methyl-diphenylamine).
実施例 ２
金属カリウム4.613ｇ（0.1180グラム原子量）、
塩化マグネシウム（無水）5.62ｇ（0.0590モル）
およびテトラヒドロフラン（THF）100mlを300
mlのフラスコ中、窒素雰囲気下でかきまぜながら
加熱還流し、反応させた。約１時間後、黒色の粉
末を生じ、金属マグネシウムが生成したことを認
めた。ついで、４，4′−ジブロモ−Ｎ−メチルジ
フエニルアミン20.12ｇ（0.0590モル）をTHF100
mlに溶解し、滴下漏斗で添加し、かきまぜながら
加熱還流し反応させた。約１時間後、金属マグネ
シウムが消費しつくされたことが認められた。次
いで、この反応生成物に触媒としてNi（dip）2Cl2
（dip：２，2′−ビピリジン）約0.10ｇを加え、か
きまぜながら加熱還流すると、重合反応が円滑に
始まつた。反応を２時間行ない、反応後、生成物
を塩酸酸性エタノール中にあけ、１時間かきまぜ
た後濾別した。フイルター上で十分にエタノール
で洗浄した後、ソツクスレー抽出器によりエタノ
ールで５時間抽出し、不純物を除去した。生成し
た重合体の乾燥後の収量は7.12ｇであつた。Example 2 4.613 g (0.1180 gram atomic weight) of metallic potassium,
Magnesium chloride (anhydrous) 5.62g (0.0590mol)
and 300 ml of tetrahydrofuran (THF)
The mixture was heated to reflux and reacted in a nitrogen atmosphere in a ml flask with stirring. After about 1 hour, black powder was produced, and it was recognized that metallic magnesium had been produced. Then, 20.12 g (0.0590 mol) of 4,4'-dibromo-N-methyldiphenylamine was added to 100 mol of THF.
ml, added through a dropping funnel, and heated to reflux while stirring to react. After about 1 hour, it was observed that the metallic magnesium was completely consumed. This reaction product was then treated with Ni(dip) 2 Cl 2 as a catalyst.
When about 0.10 g of (dip: 2,2'-bipyridine) was added and heated to reflux while stirring, the polymerization reaction started smoothly. The reaction was carried out for 2 hours, and after the reaction, the product was poured into ethanol acidified with hydrochloric acid, stirred for 1 hour, and then filtered. After thoroughly washing the filter with ethanol, it was extracted with ethanol using a Soxhlet extractor for 5 hours to remove impurities. The yield of the produced polymer after drying was 7.12 g.
この重合体の赤外スペクトルを測定したとこ
ろ、実施例１のものと同じであつた。 When the infrared spectrum of this polymer was measured, it was the same as that of Example 1.
実施例 ３
実施例１において、４，4′−ジブロモ−Ｎ−メ
チルジフエニルアミンの代りに、４，4′−ジブロ
モ−Ｎ−ｎ−ブチルジフエニルアミンを合計で
22.60ｇ（0.0590モル）使用したことを除いては、
実施例１と同様に反応を行なつた。精製後、
10.52ｇの重合体が得られた。その元素分析をし
たところ、次の結果が得られた。Example 3 In Example 1, 4,4'-dibromo-N-n-butyldiphenylamine was used instead of 4,4'-dibromo-N-methyldiphenylamine in total.
Except that 22.60g (0.0590mol) was used.
The reaction was carried out in the same manner as in Example 1. After purification,
10.52 g of polymer was obtained. When the elemental analysis was carried out, the following results were obtained.
重合体の元素分析値：
炭素(C)85.7％ 水素(H)8.0％
窒素(N)6.3％
原子比はＣ：Ｈ：Ｎ＝15.9：17.8：１で理論値
（C16H17N）に近い値であつた。Elemental analysis values of the polymer: Carbon (C) 85.7% Hydrogen (H) 8.0% Nitrogen (N) 6.3% The atomic ratio is C:H:N=15.9:17.8:1, which is the theoretical value (C 16 H 17 N) The values were close.
また、赤外スペクトルからも、ポリ−Ｎ−ｎ−
ブチルジフエニルアミンであることがわかつた。 Also, from the infrared spectrum, poly-Nn-
It turned out to be butyldiphenylamine.
第１図は、実施例１で得られた重合体の熱重量
分析結果である。第２図は、同上重合体の赤外線
吸収スペクトル図である。横軸は波数
（wavenumber；cm-1）を、縦軸は透過率（％）
を示す。
FIG. 1 shows the results of thermogravimetric analysis of the polymer obtained in Example 1. FIG. 2 is an infrared absorption spectrum diagram of the same polymer. The horizontal axis is wave number (cm -1 ), and the vertical axis is transmittance (%).
shows.
Claims (1)
Ｘはハロゲンを示す）で表わされる４，4′−ジハ
ロフエニルに、金属マグネシウムを作用させ、次
いでニツケル化合物を触媒として重合することを
特徴とする下記一般式（）で表わされる４，
4′−ジフエニルアミン構造を繰り返し単位とする
重合体の製造方法。 （式中、Ｒは炭素数１〜６のアルキル基を示す）。[Claims] 1. The following general formula () (In the formula, R represents an alkyl group having 1 to 6 carbon atoms,
4,4'-dihalophenyl (X represents halogen) is reacted with metallic magnesium and then polymerized using a nickel compound as a catalyst.
A method for producing a polymer having a 4'-diphenylamine structure as a repeating unit. (In the formula, R represents an alkyl group having 1 to 6 carbon atoms).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20972986A JPS6366224A (en) | 1986-09-08 | 1986-09-08 | Polymer and electrically conductive high polymer having diphenylamine structural unit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20972986A JPS6366224A (en) | 1986-09-08 | 1986-09-08 | Polymer and electrically conductive high polymer having diphenylamine structural unit |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23224492A Division JPH072834B2 (en) | 1992-08-31 | 1992-08-31 | Conductive polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6366224A JPS6366224A (en) | 1988-03-24 |
| JPH0520454B2 true JPH0520454B2 (en) | 1993-03-19 |
Family
ID=16577672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20972986A Granted JPS6366224A (en) | 1986-09-08 | 1986-09-08 | Polymer and electrically conductive high polymer having diphenylamine structural unit |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6366224A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0294784U (en) * | 1989-01-12 | 1990-07-27 |
-
1986
- 1986-09-08 JP JP20972986A patent/JPS6366224A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6366224A (en) | 1988-03-24 |
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