JPS63223029A - Production of electrolytic oxidation polymer - Google Patents
Production of electrolytic oxidation polymerInfo
- Publication number
- JPS63223029A JPS63223029A JP5622787A JP5622787A JPS63223029A JP S63223029 A JPS63223029 A JP S63223029A JP 5622787 A JP5622787 A JP 5622787A JP 5622787 A JP5622787 A JP 5622787A JP S63223029 A JPS63223029 A JP S63223029A
- Authority
- JP
- Japan
- Prior art keywords
- naphthalenes
- polymer
- benzoquinones
- electrolytic
- solvent
- 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 16
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 230000003647 oxidation Effects 0.000 title abstract description 4
- 238000007254 oxidation reaction Methods 0.000 title abstract description 4
- 150000004054 benzoquinones Chemical class 0.000 claims abstract description 10
- 150000002790 naphthalenes Chemical class 0.000 claims abstract description 10
- 239000002841 Lewis acid Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract description 7
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 abstract description 5
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract 2
- 229910015900 BF3 Inorganic materials 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 229920000417 polynaphthalene Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- -1 polyphenylene Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AIACLXROWHONEE-UHFFFAOYSA-N 2,3-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=C(C)C(=O)C=CC1=O AIACLXROWHONEE-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はナフタレン類またはベンゾキノン類を電解酸化
重合する方法に関し、得られる電解酸化重合体は電極、
半導体等の電気的あるいは電気化学的分野材料等として
使用できる。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method of electrolytically oxidizing polymerizing naphthalenes or benzoquinones, and the electrolytically oxidizing polymer obtained can be used as an electrode,
It can be used as a material in the electrical or electrochemical fields such as semiconductors.
従来からベンゼン等の電解重合は幾つか提案されている
。例えば米国特許３．３ｔ ＡＪ ９９号明細書ではＴ
（Ｆ−ベンゼン以外系で電解、特公昭１ｌｉ−，２３７
３／！：号公報ではＲ：ａｘ：２Ａ１ｘ、 （Ｒは芳香
族化合物、Ｘは塩素または臭素）の三元錯化物を用いて
電解、特開昭１．０−．２，７ざ３７６号公報ではベン
ゼンをフリーデルクラフッ触媒を用いて電解してポリフ
ェニレンを得ている。Several methods of electrolytic polymerization of benzene and the like have been proposed so far. For example, in U.S. Patent No. 3.3t AJ 99, T
(Electrolysis in systems other than F-benzene, Special Publication Sho 1li-, 237
3/! In JP-A No. 1.0-., a ternary complex of R:ax:2A1x, (R is an aromatic compound, X is chlorine or bromine) is used for electrolysis. In No. 2,7-376, polyphenylene is obtained by electrolyzing benzene using a Friedel Krach catalyst.
しかしながら、このような方法はベンゼン以外の化合物
に通用するには、電流効率その他の点で必ずしも充分な
ものではなかった。However, such a method was not necessarily sufficient in terms of current efficiency and other aspects to be applicable to compounds other than benzene.
本発明者は、電解重合法によりナフタレン類またはベン
ゾキノン類からこれらの電解酸化重合体を得るべく検討
を行ない、本発明に到達した０
〔問題点を解決するための手段〕
すなわち、本発明の要旨は、ナフタレン類またはベンゾ
キノン類をプロトンｒＩｋまたはルイス酸の存在下溶媒
中で電解酸化１合する電解酸化重合体の製造方法にある
。The present inventor conducted studies to obtain these electrolytically oxidized polymers from naphthalenes or benzoquinones by an electrolytic polymerization method, and arrived at the present invention. is a method for producing an electrolytically oxidized polymer, in which naphthalenes or benzoquinones are electrolytically oxidized in a solvent in the presence of proton rIk or a Lewis acid.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明においては電解酸化重合をプロトン酸またはルイ
ス酸の存在下溶媒中で行なう。In the present invention, electrolytic oxidative polymerization is carried out in a solvent in the presence of a protonic acid or a Lewis acid.
プロトン酸またはルイス酸としては、三７ツ化ホウ素、
五塩化アンチモン、塩化アルミニウム、臭化アルミニウ
ム、四塩化スズ、塩化鉄、トリフルオロメタンスルホン
酸、トリフルオロ酢酸婢が好ましく挙げられ、なかでも
特に好ましいものは、三７ツ化ホウ素、五塩化アンチモ
ン、塩化アルミニウムである。As the protonic acid or Lewis acid, boron trisulfide,
Preferred examples include antimony pentachloride, aluminum chloride, aluminum bromide, tin tetrachloride, iron chloride, trifluoromethanesulfonic acid, and trifluoroacetic acid, and particularly preferred among them are boron trisulfide, antimony pentachloride, and chloride. It is aluminum.
溶媒としては、ニトロベンゼン、ニトロメタン、ジクロ
ロメタン、アセトニトリル、プロビレ／カーボネート、
水、テトラヒドロフラン、ベンゾニトリル等が挙げられ
、このうち特に好ましいものは、ニトロメタン、ニトロ
ベンゼン、ジクロロメタンである。As a solvent, nitrobenzene, nitromethane, dichloromethane, acetonitrile, propylene/carbonate,
Examples include water, tetrahydrofuran, benzonitrile, etc. Among these, particularly preferred are nitromethane, nitrobenzene, and dichloromethane.
ナフタレン類としては、下記一般式＜１）Ｒ＠
Ｒ”
（式中、ＲＳ〜Ｒ１は同一でも異なっていてもよく、水
素原子、ハロゲン、アルキル基、置換されていてもよい
フェニルまたはフェノキシ基を示す。）で表わされる化
合物を用いる。ハロゲンとしては塩素、臭素、フッ素等
が、アルキル基としてはメチル基、エチル基等の炭素数
／〜１０のものが挙げられる。またフェニルまたはフェ
ノキシ基を置換してもよい基としては、炭素数／〜１０
のアルキルまたはアルコキシ基、ハロゲンが挙げられる
。Naphthalenes have the following general formula <1) R@R'' (where RS to R1 may be the same or different and represent a hydrogen atom, a halogen, an alkyl group, an optionally substituted phenyl or phenoxy group). ) is used. Examples of the halogen include chlorine, bromine, fluorine, etc., and examples of the alkyl group include those having a carbon number of up to 10, such as a methyl group and an ethyl group. Examples of groups that may include carbon number/~10
Examples include alkyl or alkoxy groups, and halogens.
かかるナフタレン類として具体的にはす７タレ
レン、／−７０ロナフターン、／−メチルナフレ
ターン、コ、６−ジニチルナフタレン、／、ｑシフニレ
ツキシナ７タレン、コーフェニルナフタ２ン、レ
一一イソブロビルナフターン、／−クロルナフレ
ターン、コーフエノキシナ７タレンが挙げられ、これら
のうち、特に好ましくはナフタレンでらる０
またベンゾキノン類としては、下記一般式（ｎ）Ｒ＋ｏ
Ｒ＊
（式中、Ｒ７−Ｒ１１′は同一でも 異なっていてもよ
く、水素原子、ハロゲン原子、アルキル基、アルコキシ
基、置換されていてもよいフェニルまたはフェノキシ基
を示す。また、Ｒ７と２、Ｒ９とＲ″′は同時に水素以
外の上記基を示すことはない。）で表わされる化合物を
用いる。ハロゲン原子としては塩素、臭素、フッ素等が
、アルキル基としてはメチル基、エチル基等の炭素数ｌ
〜１０のもの、アルコキシ基としてはメトキシ基、エト
キシ基等の炭素数／〜１０のものが挙げられる。またフ
ェニルまたはフェノキ７基をＲ換してもよい基としては
炭素Ｗ５／〜１０のアルキルｌたはアルコキシ基、ハロ
ゲン原子が挙げられる。Specific examples of such naphthalenes include 7-talelene, /-70 lonafthane, /-methylnaphthalene, 6-dinithylnaphthalene, /, q-sifnyl naphthalene, cophenylnaphthane, and 1-isobrobyl naphthalene. Examples of the benzoquinones include the following general formula (n) R+o.
R* (In the formula, R7-R11' may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an optionally substituted phenyl or phenoxy group. Also, R7 and 2, R9 and R″' do not represent any of the above groups other than hydrogen at the same time.The halogen atoms include chlorine, bromine, fluorine, etc., and the alkyl groups include carbon atoms such as methyl and ethyl groups. number l
Examples of the alkoxy group include those having a carbon number of 10 to 10, such as a methoxy group and an ethoxy group. Examples of groups that may be substituted with R for phenyl or phenoxy groups include alkyl or alkoxy groups having 5 to 10 carbon atoms, and halogen atoms.
かかるベンゾキノン類として具体的にはベンゾキノン、
−一メチルベンゾキノン、コーメトキシベンゾキノン、
−一フエノキシベンゾキノン、−一クロロベンゾキノン
、コーフルオロベンゾキノン、２．３−ジメチルベンゾ
キノン等が挙げられ、これらのうち特に好ましい化合物
はベンゾキノンである。Specifically, such benzoquinones include benzoquinone,
-monomethylbenzoquinone, comethoxybenzoquinone,
Examples include -monophenoxybenzoquinone, -monochlorobenzoquinone, cofluorobenzoquinone, and 2,3-dimethylbenzoquinone, and among these, benzoquinone is particularly preferred.
電解酸化重合は通常の電解セルで実施される。Electrolytic oxidative polymerization is carried out in a conventional electrolytic cell.
陽極は白金族金属例えば白金、パラジウム、ルテニウム
等が好ましく、白金が特に好ましい。The anode is preferably a platinum group metal such as platinum, palladium, ruthenium, etc., with platinum being particularly preferred.
陰極は炭素、ネサガラス、白金族金属等から好ましく選
ばれる。電解の操作条件は広い範囲で可能である。温度
は一７０℃から／θＯ′Ｃまで、好ましくはθ〜よ０℃
、更に好ましくは１０〜３０℃であるーまた印加する電
圧としては約／〜１０ＯＶの範囲で変化してよいがこの
範囲以外でも可能である。また、電流密度は重合体を得
るのに必要な密度、通常はｏ、ｏｏ、’；アンペア／−
以上が適用される。この電解条件は重合液の組成に対応
して最適な電流効率を示す条件が選ばれる。電解重合に
要する時間は通電の程度、重合液の組成によっても異な
るが通常数分〜数時間である。The cathode is preferably selected from carbon, nesagalas, platinum group metals, and the like. A wide range of operating conditions for electrolysis is possible. The temperature is from -70℃ to /θO'C, preferably from θ to 0℃
, and more preferably 10 to 30° C.; the applied voltage may vary within a range of about 1 to 10 OV, but it is also possible to apply a voltage outside this range. In addition, the current density is the density necessary to obtain the polymer, usually o, oo, '; Ampere/-
The above applies. The electrolytic conditions are selected to provide optimum current efficiency in accordance with the composition of the polymerization solution. The time required for electrolytic polymerization varies depending on the degree of energization and the composition of the polymerization solution, but is usually from several minutes to several hours.
電解液中のナフタレン類、ベンゾキノン類の量は０．０
／ ｍｏｌ／ｌ〜３ ｍｏｌ／１％ プロトン酸、ル
イス酸の量は０．０ ！ｒ ｍｏｌ／ｌ〜？ ｍｏｌ／
ｌが通常適用される。The amount of naphthalenes and benzoquinones in the electrolyte is 0.0
/ mol/l ~ 3 mol/1% The amount of protonic acid and Lewis acid is 0.0! r mol/l~? mol/
l is usually applied.
電解酸化重合によシナ７タレン類、ベンゾキノン類は陽
極上にポリナフタレン類、ポリベンゾキノン類が生成す
る。この重合膜は通電時間を長くすることによシ膜厚を
調整することも可能である。得られる重合物は必要によ
シ水、希塩酸、メタノール等で洗浄される。By electrolytic oxidation polymerization, polynaphthalenes and polybenzoquinones are produced from the sina7talenes and benzoquinones on the anode. The thickness of this polymeric film can also be adjusted by lengthening the energization time. The obtained polymer is washed with water, dilute hydrochloric acid, methanol, etc., if necessary.
本発明方法で得られるポリナフタレン類は、下記一般式
（１）で示されるポリ／、ターナフタレン構造を有する
新規重合体である。The polynaphthalenes obtained by the method of the present invention are novel polymers having a poly/turnaphthalene structure represented by the following general formula (1).
て式中、Ｒ１−Ｒ１は前記一般式（１）と同義である。In the formula, R1-R1 has the same meaning as in the above general formula (1).
）また、本発明方法で得られるポリベンゾキノン類も下
記一般式（ｆＶ）で示されるポリベンゾキ（式中、Ｒ７
〜Ｒ１Ｇは前記一般式（ＩＩ）と同義である。）
〔発明の効果〕
本発明方法によれば、ナフタレン類およびベンゾキノン
類を容易に高電解効率で得ることができ、また得られる
ポリナフタレン類およびポリベンゾキノン類は電極、牛
導体尋の電気、電気化学用材料として有用である。) Moreover, the polybenzoquinones obtained by the method of the present invention are also polybenzoquinones represented by the following general formula (fV) (in the formula, R7
~R1G has the same meaning as the general formula (II) above. ) [Effects of the Invention] According to the method of the present invention, naphthalenes and benzoquinones can be easily obtained with high electrolytic efficiency, and the polynaphthalenes and polybenzoquinones obtained can be used in electrodes, electrical conductors, and electrical applications. Useful as a chemical material.
以下実施例により本発明を更に詳細に説明する０
実施例／
ｐ−ベンゾキノン／、７３１１無水塩化アルミニウム／
０．１．りｌｉト水０．／Ｊｉヲニトロメタン７！−
に溶解し、窒素ガスを通気し脱酸素する。The present invention will be explained in more detail with reference to Examples below.0 Example/p-benzoquinone/, 7311 Anhydrous aluminum chloride/
0.1. Lit water 0. /Jiwonitromethane 7! −
and deoxidize by blowing in nitrogen gas.
これに白金板（λ×５−）コ板を７百間隔で対面設置し
、設定電流ｊ ＯｍＡにてコｒｏｏｃ電解した。陽極上
に黒色のポリマー薄膜が生成し、水−メタノールで洗浄
しポリマーを収率６％で得たＯ
工Ｒスペクトルν ／６弘Ｏ１／６コｏｔｍ’Ｃ七
〇
元素分析値（理論値） Ｏ： １，７．ｔ （Ａ７．
９） 。Platinum plates (λ×5−) were placed facing each other at intervals of 700, and corooc electrolysis was performed at a set current of j OmA. A black polymer thin film was formed on the anode and washed with water-methanol to obtain a polymer with a yield of 6%. O: 1,7. t (A7.
9).
Ｈ：／、３２（ハざｔ）
よシボリペンゾキノンの構造を確認した０得られたポリ
ベンゾキノ／の工Ｒ吸収スペクトルを第１図に示す。H:/, 32 (Hazat) Figure 1 shows the R absorption spectrum of the obtained polybenzoquinone, which confirmed the structure of the penzoquinone.
実施例コ
ｐ−ベンゾキノンハク３１１．三７ツ化ホウ素ジエチル
エーテル／ｒｍｔｔニトロベンゼン溶液（Ａｄｊｎｔ）
に溶解させた。これに白金板（，２Ｘｊ ｃｍ ） ２
枚を／７ｍ間隔で対面設置した０設定電位／、ｇＶにて
ハ＆Ｆ／ｍｏｌ電解した。陽極上に黒色のポリマー膜を
得た。膜をメタノールで洗浄、収量はｏ、ｉ ｔ ｇで
あった。Example Co p-Benzoquinone Haku 311. Boron trisulfide diethyl ether/rmtt nitrobenzene solution (Adjnt)
It was dissolved in Platinum plate (,2Xj cm) 2
The sheets were placed facing each other at an interval of /7 m and electrolysis was carried out at a potential of 0/gV. A black polymer film was obtained on the anode. The membrane was washed with methanol, yield was o, it g.
工Ｒスペクトルν（：＝Ｑ ／Ａ’ＩＯ、／４２０．
”元素分析値（理論値） Ｏ： ／、４．Ａ（Ａり、
９）。Engineering R spectrum ν(:=Q /A'IO, /420.
”Elemental analysis value (theoretical value) O: /, 4.A (Ari,
9).
１（： ／、７２ （／、ざざ）
実施例３
す７タレンｔ、／１１１、無水塩化アルミニウム／θ、
６りｉと水ｏ、ｉ ｔｉをニトロメタン７ｊ−に。1 (: /, 72 (/, Zaza) Example 3 Su7 talent t, /111, anhydrous aluminum chloride /θ,
6ri i, water o, i ti to nitromethane 7j-.
溶解し、窒素ガスを通気し脱酸素する。これに白金板（
，２Ｘｊｃｒｎ）コ板を／帰間隔で対面設置し、設定電
流θ、ｊＡにて０．Ａ Ｐ／ｍｏｌ電解した。Dissolve and deoxidize by bubbling nitrogen gas. Add this to the platinum plate (
, 2 AP/mol was electrolyzed.
陽極上に茶褐色のポリマーが生成し、水−メタノールで
洗浄してポリマーを電流効率３７％で得た。A brownish polymer was formed on the anode and washed with water-methanol to obtain a polymer with a current efficiency of 37%.
工Ｒスペクトルν ／＆２０ 、 ／！；００ 、
ｉコｏ 、 ／ａｔＯｃｒｎ−’ＷＣ
δ ｇコ０．７１．０の−１
−Ｈ
よりポリナフタレンの構造を確認した。Engineering R spectrum ν /&20, /! ;00,
The structure of polynaphthalene was confirmed from -1-H of icoo, /atOcrn-'WC δ gco0.71.0.
得られたポリナフタレンのＩＲ吸収スペクトルを第一図
に示す。The IR absorption spectrum of the obtained polynaphthalene is shown in Figure 1.
実施例ダ
ナフタレン７．／ＩＩ、五塩化アンチモン／、！ｒ−を
ニトロベンゼンｌ−！；ｒｄに溶解した。これに白金板
（コＸ ！ ｃｍ ）一枚を／（ｍ間隔で対面設置し、
設定電位２．ＯＶ （ＶＳ Ａｇ／Ａｇ０１ ）にて／
Ｆ／ｍｏｌ電解した。陽極上にポリマーが生成、水−メ
タノール洗浄後／、ざＩ得た。Example Danapthalene7. /II, antimony pentachloride/,! r- to nitrobenzene l-! ;Dissolved in rd. On this, one platinum plate (X! cm) was installed facing each other at /(m intervals,
Set potential 2. At OV (VS Ag/Ag01)/
F/mol was electrolyzed. A polymer was formed on the anode, and after washing with water and methanol, a residue was obtained.
工Ｒスペクトルν ／ｌ、、ｔＯ、／！００ 、バー
’ ＋ ／ Ｊ ’０６Ｎ−’−Ｃ
”Ｃ−１（ｇ−〇、７６θの−１
よシボリナ７タレン構造を確認した。Engineering R spectrum ν /l,,tO,/! 00, bar'+/J'06N-'-C''C-1 (g-〇, -1 of 76θ), the Cibolina 7-talene structure was confirmed.
実施例！
ナフタレン、Ｉ、！ ９１！、三フフ化ホウ素ジエチル
エーテル１５−をニトロメタン６！−に溶解した。これ
に白金板（コ×！譚）一枚を／の間隔で設置した。定電
位２００ ｍＡにてＡ、ｊ Ｆ／ｍａ１電解した。陽極
上に茶褐色のポリマーが生成、メタノール洗浄後θ、！
ｒ／ Ｆ得た。Example! Naphthalene, I! 91! , boron trifluoride diethyl ether 15- to nitromethane 6! - dissolved in On top of this, one platinum plate (Ko×!tan) was installed at intervals of /. A, j F/ma1 electrolysis was performed at a constant potential of 200 mA. A brown polymer is formed on the anode, θ after methanol cleaning!
I got r/F.
工Ｒスペクトルν ／１ｓ２０ 、 ／１００ 、
／４＜２（’ ＋ ／ ｊ ７０Ｃｍ−’−Ｃ
δ ざコ’ ｌ ｔ＆０ＣＲ−’
−ＣEngineering R spectrum ν /1s20, /100,
/4<2(' + / j 70Cm-'-C δ Zako' l t&0CR-' -C
第７図は実施例／のポリベンゾキノンのＸＲ吸収スペク
トル図、第一図は実施例３のポリナフタレンの工Ｒ吸収
スペクトルを示す。
出 願 人 三菱化成工業株式会社
代 理 人 弁理士長香川 −
ほか／名FIG. 7 shows the XR absorption spectrum of the polybenzoquinone of Example 3, and FIG. 1 shows the XR absorption spectrum of the polynaphthalene of Example 3. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Nagakagawa - Others/Names
Claims (1)
酸またはルイス酸の存在下、溶媒中で電解酸化重合する
ことを特徴とする電解酸化重合体の製造方法。(1) A method for producing an electrolytically oxidized polymer, which comprises electrolytically oxidizing and polymerizing naphthalenes or benzoquinones in a solvent in the presence of a protonic acid or a Lewis acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5622787A JPH0749470B2 (en) | 1987-03-11 | 1987-03-11 | Method for producing electrolytically oxidized polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5622787A JPH0749470B2 (en) | 1987-03-11 | 1987-03-11 | Method for producing electrolytically oxidized polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63223029A true JPS63223029A (en) | 1988-09-16 |
| JPH0749470B2 JPH0749470B2 (en) | 1995-05-31 |
Family
ID=13021219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5622787A Expired - Lifetime JPH0749470B2 (en) | 1987-03-11 | 1987-03-11 | Method for producing electrolytically oxidized polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0749470B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07247344A (en) * | 1994-03-14 | 1995-09-26 | Tokyo Inst Of Technol | Polyquinone, its production, and material for electrochromic element or for n-type semiconductor device containing the same |
| JP2006342339A (en) * | 2005-05-09 | 2006-12-21 | Sumitomo Chemical Co Ltd | Aromatic polymer and method for producing the same |
-
1987
- 1987-03-11 JP JP5622787A patent/JPH0749470B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07247344A (en) * | 1994-03-14 | 1995-09-26 | Tokyo Inst Of Technol | Polyquinone, its production, and material for electrochromic element or for n-type semiconductor device containing the same |
| JP2006342339A (en) * | 2005-05-09 | 2006-12-21 | Sumitomo Chemical Co Ltd | Aromatic polymer and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0749470B2 (en) | 1995-05-31 |
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