JPS62197421A - Production of benzene polymer - Google Patents
Production of benzene polymerInfo
- Publication number
- JPS62197421A JPS62197421A JP3819386A JP3819386A JPS62197421A JP S62197421 A JPS62197421 A JP S62197421A JP 3819386 A JP3819386 A JP 3819386A JP 3819386 A JP3819386 A JP 3819386A JP S62197421 A JPS62197421 A JP S62197421A
- Authority
- JP
- Japan
- Prior art keywords
- benzene
- electrolyte
- transition metal
- electrolytic
- mol
- 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.)
- Pending
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 22
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 abstract description 14
- 150000001768 cations Chemical class 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000002841 Lewis acid Substances 0.000 abstract description 5
- 150000007517 lewis acids Chemical class 0.000 abstract description 5
- 235000010290 biphenyl Nutrition 0.000 abstract description 4
- 239000004305 biphenyl Substances 0.000 abstract description 4
- 125000006267 biphenyl group Chemical group 0.000 abstract description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000010 aprotic solvent Substances 0.000 abstract description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 150000002892 organic cations Chemical class 0.000 abstract description 2
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 abstract 1
- 229910017048 AsF6 Inorganic materials 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].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 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- -1 polyphenylene Polymers 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 5
- 229920000265 Polyparaphenylene Polymers 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229930184652 p-Terphenyl Natural products 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
「技術分野」
本発明は、ベンゼンの重合体の分野に属するもので、該
高分子の電気化学的な製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention belongs to the field of benzene polymers, and relates to an electrochemical method for producing the polymers.
「従来技術」
ベンゼン重合体は、安定でかつ耐熱性が高く、ｐ型、ｎ
型ドーピングが可能であり、耐熱性高分子材料、導電性
高分子材料として注目されている。"Prior art" Benzene polymer is stable and has high heat resistance, and has p-type, n-type
Type doping is possible, and it is attracting attention as a heat-resistant polymer material and a conductive polymer material.
ベンゼン重合体は、化学的合成法で得られるが、前者は
生成物が粉状であって膜状にするためには焼結法等によ
り成形加工しなければならない。ベンゼンまたはその誘
導体より直接膜状ベンゼン重合体を合成する方法として
は、例えば、Ｊ、 Ｐｏｌｙｗ。Benzene polymers can be obtained by chemical synthesis, but the former product is in powder form and must be shaped into a film by sintering or the like. As a method for directly synthesizing a film-like benzene polymer from benzene or its derivatives, for example, J. Polyw.
Ｓｃｉ、 Ａ−１，４，５１１（１９６６）にＨＦ−ベ
ンゼンの二相系での電解合成が；米国特許第３，４３７
，５６９号明細書、同第３．４３７，５７０号明細書に
はメシチレン：ＨＣｌ： ２ＡＩＣ１２系での電解合成
が； Ｂｌｅｃｔｒｏ−ｃｈｅｍ、 Ａｃｔａ、、 ２
７．６Ｎ１９Ｂ２）には液体Ｓ０２中での電解合成が；
Ｅｌｅｃｔｒｏｃｈｅｍ、 Ａｃｔａ、＋ １２９＋
１９５０（１９８２）にはＨＦ／Ｓ ｂ Ｆ、スーパー
アシッド存在下での電解合成が； Ｊ、 Ｃｈｅｍ、Ｓ
ｏｃ、＋Ｃｈｅａ＋、 Ｃｏｍｍｕｎ、＋１１９９（１
９８４）にはＡｊｌＣＩ存在下での電解合成が報告され
ている。また、Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ
Ｓｃｉｅｎｃｅ： Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒ
ｙ Ｅｄｉｔｉｏｎ、 Ｖｏｌ、 ２１＋３０３５−３
０４０ （１９８３）には、ＨＦ／ベンゼン系により得
られるポリフェニレン膜がアモルファスであることが報
告されている。Sci. A-1,4,511 (1966) describes electrolytic synthesis of HF-benzene in a two-phase system; U.S. Pat. No. 3,437.
, 569 and 3,437,570 describe electrolytic synthesis in mesitylene:HCl:2AIC12 system; Blectro-chem, Acta, 2
7.6N19B2) has electrolytic synthesis in liquid S02;
Electrochem, Acta, +129+
1950 (1982), electrolytic synthesis in the presence of HF/S b F, superacid; J, Chem, S.
oc, +Chea+, Common, +1199 (1
(984) reported electrolytic synthesis in the presence of AjlCI. Also, Journal of Polymer
Science: Polymer Chemistry
y Edition, Vol, 21+3035-3
040 (1983), it is reported that the polyphenylene film obtained by the HF/benzene system is amorphous.
本発明者らは、先にポリフェニレン類を負極活物質とし
て用いる電池を提案しく特願昭６０−１７２０３５号）
、この中でフリーゾルタラフッ型触媒を用いる重合系が
膜状ポリフェニレンを得るのに有効であることを述べた
。ＦｅＣｊ！ｚ、Ａｌｃｆｆ、１．ＺｎＣＮｚ、ＡｇＢ
ｒｚなどのルイス酸あるいはこれらの錯体が系の中で電
解質塩として働き、少な（ともモノマー（ベンゼンまた
はその誘導体）、溶媒、電解質からなる系で重合できる
ことを示した。The present inventors previously proposed a battery using polyphenylenes as a negative electrode active material (Japanese Patent Application No. 172035/1982).
In this paper, it was stated that a polymerization system using a free-sol fluorine catalyst is effective for obtaining membrane-like polyphenylene. FeCj! z, Alcff, 1. ZnCNz, AgB
It was shown that Lewis acids such as rz or their complexes function as electrolyte salts in the system, and that polymerization can be achieved in a system consisting of a small amount of monomer (benzene or its derivative), solvent, and electrolyte.
しかし、十分な膜厚の均質性の良好な高い伝導度のベン
ゼン重合体膜を得るに至っていない。また、反応が酸性
の強い過酷な反応系で行われる等の問題があった。However, a benzene polymer film with sufficient uniformity of film thickness and high conductivity has not yet been obtained. Further, there were problems such as the reaction being carried out in a harsh and highly acidic reaction system.
「目的」
本発明の目的は、これらの問題点を解決し、高い電導度
で、均質で充分な膜厚を持ったベンゼン重合体を、過酷
な反応系を用いることなく、電気化学的に得ることにあ
る。"Objective" The purpose of the present invention is to solve these problems and to electrochemically obtain a benzene polymer with high conductivity, homogeneity, and sufficient film thickness without using a harsh reaction system. There is a particular thing.
「構成」
本発明者らは、特願昭６０−２７１０７８号において、
ルイス酸の錯体を用いることにより、均質性が向上した
ベンゼン重合体が形成されることを提案した。この知見
にもとすき、さらに錯体の存在下におけるベンゼンの電
解酸化によるベンゼン重合体合成を鋭意検討し、錯体と
して遷移金属錯体の存在下に反応を行うことにより、高
い電導度の均質なベンゼン重合体の膜を陽極面上で得る
ことができ、本発明に至った。"Configuration" The present inventors, in Japanese Patent Application No. 60-271078,
We proposed that benzene polymers with improved homogeneity could be formed by using complexes of Lewis acids. Based on this knowledge, we further investigated the synthesis of benzene polymers by electrolytic oxidation of benzene in the presence of a complex, and by carrying out the reaction in the presence of a transition metal complex as a complex, we were able to produce a homogeneous benzene polymer with high conductivity. A coalescent film could be obtained on the anode surface, leading to the present invention.
即ち、本発明は、ベンゼンまたはその誘導体を電気化学
的に重合してベンゼン重合体を製造する方法において、
重合を遷移金属錯体の存在下で行うことを特徴とするベ
ンゼン重合体の製造方法についてのものである。That is, the present invention provides a method for producing a benzene polymer by electrochemically polymerizing benzene or a derivative thereof.
This invention relates to a method for producing a benzene polymer, characterized in that polymerization is carried out in the presence of a transition metal complex.
また、本発明でのベンゼン重合体とは、ポリフェニレン
のような線状重合体はもとより、ポリアセン、ポリアセ
ンセン類似の面状重合体も含まれるものである。Furthermore, the benzene polymer in the present invention includes not only linear polymers such as polyphenylene, but also polyacene and planar polymers similar to polyacene.
本発明を更に詳しく述べる。The present invention will now be described in more detail.
本発明は、陽極および陰極を備えた電解槽に原料のベン
ゼンまたはベンゼン誘導体、電解質、および遷移金属錯
体を溶媒に溶かした電解液中で電解酸化を行い、陽掘上
にベンゼン重合体を生成析出させるものである。The present invention performs electrolytic oxidation in an electrolytic solution containing benzene as a raw material or a benzene derivative, an electrolyte, and a transition metal complex dissolved in a solvent in an electrolytic cell equipped with an anode and a cathode, and produces and precipitates a benzene polymer on a positive excavation. It is something that makes you
本発明に用いられる重要な因子である遷移金属錯体とは
、狭義にはＮｉ、Ｃｏ、Ｃｕｓ Ｃｒ、、Ｍｎ、Ｆ ｅ
％ Ｚ ｎなどの遷移金属を有する錯体で、広義には
遷移金属の配位化合物に及ぶものであり、例えばＮ ｉ
Ｃ１ｚＣＰ Ｐ ｈ３）ｚ 、Ｎ ｉ Ｃ１ｔＣＰ
Ｐ ｈｔ（ａｌｌｙｌ））ｚ、Ｎ ｉ Ｃｌ ｔ（Ｐ
Ｐ ｈ （ａｌｌｙｌ））ｚ 、Ｃ。Transition metal complexes, which are important factors used in the present invention, include Ni, Co, Cus Cr, Mn, Fe
%Z A complex containing a transition metal such as n, and in a broad sense it covers coordination compounds of transition metals, for example, N i
C1zCP P h3)z, N i C1tCP
P ht(allyl)z, N i Cl t(P
P h (allyl)z, C.
Ｃ１ｘ（Ｐ Ｐ ｈｉ）ｚ 、ＣＯＣｊ！ｚ（Ｐ Ｐ
ｈｚ（ａｌｌｙｌ））ｚｌＣｏ Ｃｌ ｚ（Ｐ Ｐ ｈ
（ａｌｌｙｌ）ｚ）ｔ、Ｃｏ （ＮＨｉ）ｚ（ＮＯｘ
）ｉ 、Ｍｎ （ＮＨｓ）ａ（ＮＯｓ）ｚ 、Ｃｒ
（ＮＨ３）＆（ＮＯｚ ） ｔ −、Ｓ ｎ （ＮＨ３
）ｉ（ＮＣｈｈなどが挙げられる。電解液中の該錯体の
使用量は、０．００１〜１．０ｍｏｌ＃！が好ましいが
、特にこの範囲゛に限定されるものではない。C1x(P P hi)z, COCj! z(P P
hz(allyl)zlCo Cl z(P P h
(allyl)z)t, Co (NHi)z(NOx
)i, Mn (NHs)a(NOs)z, Cr
(NH3)&(NOz)t-,Sn(NH3)
)i(NChh, etc.) The amount of the complex used in the electrolytic solution is preferably 0.001 to 1.0 mol#!, but is not particularly limited to this range.
本発明に用いられる原料モノマーとしては、ベンゼン、
ジフェニル、ｐ−ターフェニル、０−ターフェニル、ｍ
−ターフェニル、ナフタリン、アンスラセン等の芳香族
炭化水素等およびそれらのハロゲン（Ｆ、Ｃｒ、Ｂｒ、
Ｉ）およびアルキル（炭素数１〜３）の置換体を挙げる
ことができる。The raw material monomers used in the present invention include benzene,
diphenyl, p-terphenyl, 0-terphenyl, m
- Aromatic hydrocarbons such as terphenyl, naphthalene, anthracene, etc. and their halogens (F, Cr, Br,
I) and alkyl (1 to 3 carbon atoms) substituents.
この中で、ベンゼン、ジフェニルが望ましいものである
。電解液中のモノマーの使用量は、０．０５〜１．Ｏｍ
ｏｌ／ ｌが好ましい範囲である。Among these, benzene and diphenyl are preferred. The amount of monomer used in the electrolyte is 0.05 to 1. Om
The preferred range is ol/l.
本発明に用いられる電解質は、本発明の特徴である遷移
金属錯体を用いることにより、一般的な電解反応におけ
るのとは異なり制限される。即ち電解質塩のカチオンは
、Ｎ ａ ” 、Ｋ ” 、Ｌ ｉ”、Ａｇ０などの金
属カチオン、テトラブチルアンモニウム、テトラエチル
アンモニウムなどのアルキルアンモニウムなどの有機物
カチオン、アニオンは、Ａｓ Ｆｂ−、ＰＦｂ−、ＢＦ
４−．５ｂＦａ−などルイス酸を生成しうるアニオンで
ある。これらカチオンとアニオンの組合せよりなる電解
質塩が有効である。例えばＬｉＰＦｂ、Ｌｉ５ｂＦ、、
、Ｌ ｉＡ Ｓ Ｆ ６ 、Ｋ Ｐ Ｆ ＆ 、Ｋ Ｓ
ｂ Ｆ ６ 、Ａ ｇ Ｂ Ｆ ４、ＮａＢＦ４、Ｎ
ａＡｓ Ｆｂ 、Ｎａ ＰＦｂ、（（ｎ−Ｂｕ）４Ｎ）
・（Ａ ｓ Ｆｂ ）、（（ｎ −Ｂｕ）４Ｎ）
・Ｂ Ｆ ａ、（（ｎ Ｂｕ）ｔＮ） ・Ｐ Ｆ
ｂ、（（ｎ−Ｂｕ）４Ｎ）・ＳｂＦ、、（（ｎ −ｐｔ
）ｔＮ） ・Ｂ Ｆ、などがある（Ｂｕはブチル基、
Ｅｔはエチル基を示す）。Due to the use of a transition metal complex, which is a feature of the present invention, the electrolyte used in the present invention is limited unlike that in general electrolytic reactions. That is, the cations of the electrolyte salt include metal cations such as Na'', K'', Li'', and Ag0, organic cations such as alkylammonium such as tetrabutylammonium and tetraethylammonium, and the anions include AsFb-, PFb-, and BF.
4-. It is an anion capable of producing a Lewis acid such as 5bFa-. Electrolyte salts consisting of a combination of these cations and anions are effective. For example, LiPFb, Li5bF,
, L iA S F 6 , K P F & , K S
b F 6 , A g B F 4, NaBF4, N
aAsFb, NaPFb, ((n-Bu)4N)
・(A s Fb ), ((n -Bu)4N)
・B F a, ((n Bu) tN) ・P F
b, ((n-Bu)4N)・SbF,, ((n-pt
)tN) ・BF, etc. (Bu is a butyl group,
Et represents an ethyl group).
電解液中の電解質の使用量は、０．０１〜１．０ｍｏｌ
／ ｌが好ましい範囲である。The amount of electrolyte used in the electrolytic solution is 0.01 to 1.0 mol
/l is a preferred range.
電解質溶媒としては、例えばアセトニトリル、ベンゾニ
トリル、プロピレンカーボネート、γ−ブチロラクトン
、ジクロルメタン、ジクロルエタン、ジメチルホルムア
ミド、ニトロメタン、ニトロエタン、ニトロベンゼンな
どの非プロトン性溶媒を挙げることができる。好ましい
溶媒としては、ニトロメタン、ニトロエタン、ニトロベ
ンゼン、ジクロルエタン、ジクロルメタンなどのドナー
性の低い溶媒（ドナー数約１０以下）を用いたものが挙
げられる。Examples of the electrolyte solvent include aprotic solvents such as acetonitrile, benzonitrile, propylene carbonate, γ-butyrolactone, dichloromethane, dichloroethane, dimethylformamide, nitromethane, nitroethane, and nitrobenzene. Preferred solvents include those using solvents with low donor properties (approximately 10 or less donors) such as nitromethane, nitroethane, nitrobenzene, dichloroethane, and dichloromethane.
電解重合時の電極を構成する材料としては、例えばＡｕ
５ｐｔ、Ｎｉ等の金属、Ｓｎｏｗｌ Ｉｎｇｏ、などの
金属酸化物、これらの複合電極またはコーティング電極
を挙げることができ、特に金属酸化物を陽極に用いると
、強度のあるベンゼン重合体膜が得られるので好ましい
。As a material constituting the electrode during electrolytic polymerization, for example, Au
Examples include metals such as 5pt, Ni, metal oxides such as Snowl Ingo, and composite electrodes or coated electrodes of these. In particular, when metal oxides are used for the anode, a strong benzene polymer film can be obtained. preferable.
電解槽は同一電解槽中に陽極および陰極を備えた単一電
解槽、および陽極および陰掻間を隔膜分離した電解槽が
使用される。しかし、単一電解槽で容易に本発明を実施
できる。As the electrolytic cell, a single electrolytic cell having an anode and a cathode in the same electrolytic cell, and an electrolytic cell in which the anode and the negative electrode are separated by a diaphragm are used. However, the present invention can be easily practiced with a single electrolytic cell.
電解としては、定電圧電解、定電流電解、定電位電解の
いずれも可能であるが、定電流、定電位による電解が適
しており、特に量産の面からは定電流電解が好ましい。As the electrolysis, any of constant voltage electrolysis, constant current electrolysis, and constant potential electrolysis are possible, but constant current and constant potential electrolysis are suitable, and constant current electrolysis is particularly preferred from the standpoint of mass production.
電流密度の調整は、膜のモルフォロジーに大きな影響を
与えるので重要であり、電解液の成分の組合せによって
微妙に変化する。電解密度は特に制限されるものではな
いが、０．１〜３０ｍＡ／ｃｍ”で好ましく行われる。Adjustment of the current density is important because it has a large effect on the morphology of the membrane, and it changes subtly depending on the combination of electrolyte components. Although the electrolytic density is not particularly limited, it is preferably 0.1 to 30 mA/cm''.
本発明で得られたベンゼン重合体は、化学的或いは電気
化学的に脱ドープした膜にすることができる。更に、こ
れに新たなドーパントをドープすることができる。これ
は、例えば、Ｉｔ、Ｂｒｚ、Ｃ１，、ＡｓＦ、 、５ｂ
Ｆｓなどのルイス酸、ＦＳＯｚＨ，ＨＮＯｚ 、ＣＦ３
５０３ＨＳＨｉｓＯｓなどのブレンステッド酸によるド
ーピング、あるいはＬ ｉ” ｓ Ｎ ａ ”″、Ｋ″
″、Ａｇ” 、ＥｔＮ４”、ＢｕａＮ＋などのカチオン
と、ｃｔｏ４− 、ＢＦ４−１ＰＦ、−１ＡｓＦ、−な
どのアニオンとの組合せからなる塩を溶解させた電解質
溶液中における電気化学的ドーピングなどにより、行う
ことができる。このようにして広い範囲の各種のドーパ
ントを持ったベンゼン重合体を生成することが出来る。The benzene polymer obtained in the present invention can be made into a chemically or electrochemically dedoped film. Furthermore, it can be doped with new dopants. This is, for example, It, Brz, C1,, AsF, , 5b
Lewis acids such as Fs, FSOzH, HNOz, CF3
Doping with Brønsted acids such as 503HSHisOs or L i”s N a “”, K”
This is carried out by electrochemical doping in an electrolyte solution in which a salt consisting of a combination of cations such as ", Ag", EtN4", BuaN+, and anions such as cto4-, BF4-1PF, -1AsF, - is dissolved. In this way, benzene polymers with a wide variety of dopants can be produced.
本発明により得られたベンゼン重合体膜は、自己保持性
の良い均質な膜である。The benzene polymer film obtained by the present invention is a homogeneous film with good self-retention properties.
「効果」
本発明の方法はベンゼン重合体を合成するのに、遷移金
属錯体の存在下に電解酸化を行う新規な方法を提供する
ものである。更に、本発明により今まで各種の電解酸化
では難しかった、高い電気型導度をもつ均質なベンゼン
重合体膜が生成でき、電極材料、半導体材料、エレクト
ロクロミック材料、電磁シールド材料等への応用が可能
である。"Effects" The method of the present invention provides a novel method of performing electrolytic oxidation in the presence of a transition metal complex to synthesize a benzene polymer. Furthermore, the present invention makes it possible to produce a homogeneous benzene polymer film with high electrical conductivity, which has been difficult until now with various electrolytic oxidations, and can be applied to electrode materials, semiconductor materials, electrochromic materials, electromagnetic shielding materials, etc. It is possible.
以下、実施例を挙げて本発明を具体的に説明する。The present invention will be specifically described below with reference to Examples.
「実施例」
実施例１゜
陽極にネサガラス（３０ｏｈｍ ／ ｃｌｌｌ） 、陰
極にニッケルを備えた単一電解槽に、ベンゼン（０，１
モル） 、Ｎ ｉ Ｃ１ｚ（Ｐ Ｐ ｈ（ａｌｌｙｌ）
） ｚ （０，０１モル）及びＢｕ４Ｎ−ＢＦ４ （
０，１モル）をニトロベンゼン（全容量１１）に溶かし
た電解液を入れ、電流密度１５ｍＡ／ｃｄ で０．５
時間、定電流電解を行い、陽極のネサガラスの表面上に
ベンゼン重合体の濃褐色の光沢ある均質な膜を得た。"Example" Example 1゜Benzene (0,1
mole), N i C1z(P Ph(allyl)
) z (0,01 mol) and Bu4N-BF4 (
Add an electrolytic solution containing 0.1 mol) dissolved in nitrobenzene (total capacity 11), and add 0.5 mol) at a current density of 15 mA/cd.
Constant current electrolysis was carried out for several hours, and a dark brown, glossy, homogeneous film of benzene polymer was obtained on the surface of the Nesaglass anode.
このものは膜厚４３μｍで、電気型導度（σ）は２．５
Ｘ １０−’Ｓ／ ｅｌｍ （成長直後）であった。This film has a film thickness of 43 μm and an electrical conductivity (σ) of 2.5.
X 10-'S/elm (immediately after growth).
また、生成膜のＩＲ（透過）；ｅｏｏ〜８００（６９０
，７６０，８００）ａｒｍ−’、および１００９ｃｍ−
’から芳香核が主体の高分子である。In addition, IR (transmission) of the produced film; eoo ~ 800 (690
, 760, 800) arm-', and 1009 cm-
It is a polymer mainly composed of aromatic nuclei.
実施例２゜
実施例１と同じ電解槽に、ベンゼン（０，１モル）とＮ
ｉＣβｚ （Ｐ Ｐ ｈｚ）ｚ （０，１モル）及び
ＢｕｓＮ−ＰＦｈ （０，１モル）をニトロベンゼン（
全容量１１）に溶かした電解液を入れた後Ａｒガス雰囲
気下（０□ ：１ｐｐｎ＋以下、露点−一８１℃）に電
流密度１ｍＡ／ｃ＋４で８時間、定電流電解を行ってベ
ンゼン重合体を合成した。ベンゼン、ニトロベンゼンは
、モレキュラシープで脱水した後、真空蒸溜したものを
使用した。Example 2゜In the same electrolytic cell as in Example 1, benzene (0.1 mol) and N
iCβz (P P hz)z (0.1 mol) and BusN-PFh (0.1 mol) in nitrobenzene (
After adding the dissolved electrolyte to the total capacity 11), constant current electrolysis was performed at a current density of 1 mA/c + 4 for 8 hours under an Ar gas atmosphere (0□: 1 ppn+ or less, dew point -81°C) to convert the benzene polymer. Synthesized. Benzene and nitrobenzene were dehydrated with a molecular sheep and then vacuum distilled.
膜厚：４２μｍ−、ｔｌ： １．６Ｘ１０Ｓ／（Ｊ（成
長直後）。Film thickness: 42 μm-, tl: 1.6×10S/(J (immediately after growth).
実施例３゜
実施例１と同じ電解槽に、ベンゼン（０，１モル）とＣ
ＯＣ１ｚｃＰ Ｐ ｈｚ）ｚ （０，２モル）及びＢ
ｕ、Ｎ−ＢＦ４ （０，１モル）とをニトロベンゼン（
全容量１１）に溶かした電解液を入れた後、２０Ｖの定
電圧電解を０．５時間行って、ベンゼン重合体膜を合成
した。Example 3 In the same electrolytic cell as in Example 1, benzene (0.1 mol) and C
OC1zcP P hz)z (0,2 mol) and B
u, N-BF4 (0.1 mol) and nitrobenzene (
After filling the total volume 11) with the dissolved electrolyte solution, constant voltage electrolysis at 20V was performed for 0.5 hours to synthesize a benzene polymer film.
膜厚：２９μｍ、 ｅｆ：５．３Ｘ１０−’Ｓ／ａｍ（
成長直後）。Film thickness: 29μm, ef: 5.3X10-'S/am (
immediately after growth).
実施例４゜
実施例１と同じ電解槽に、ベンゼン（０，１モル）とＣ
ｏ（ＮＨｓ）ｓ （Ｎｏｔ）ｓ （０，０２モル）及び
Ｂｕ ４ Ｎ−Ａ ｓ Ｆ ｈ （０、１モル）とをニ
トロベンゼン（全容量１１）に溶かした電解液を入れた
後、空気中で１５ｍＡ／−で０．５時間、定電流電解を
行ってベンゼン重合体を合成した。Example 4 In the same electrolytic cell as in Example 1, benzene (0.1 mol) and C
After adding an electrolyte solution in which o(NHs)s (Not)s (0.02 mol) and Bu 4 N-A s F h (0.1 mol) were dissolved in nitrobenzene (total volume 11), it was placed in the air. Constant current electrolysis was performed at 15 mA/- for 0.5 hours to synthesize a benzene polymer.
膜厚：４１μｍ、 ｄ ： ２．ＯＸ １０−’Ｓ／
ｃｓ（成長直後）。Film thickness: 41 μm, d: 2. OX 10-'S/
cs (immediately after growth).
実施例５゜
実施例２と同様にして電解槽に、ベンゼン（０，１モル
）とＮ ｉ Ｃｌ ｚ（Ｐ Ｐ ｈｚ）ｚ （０，１モ
ル）及びＢ ｕ４Ｎ ＨＢ Ｆ ａ （０、１モル）
とをニトロベンゼン（全容ＩＩ ｌ）に溶かした電解液
を入れた後、空気中で１ｍＡ／ａｊで８時間、定電流電
解を行ってベンゼン重合体を合成した。Example 5 In the same manner as in Example 2, benzene (0.1 mol), N i Cl z (P P hz) z (0.1 mol) and Bu4N HB Fa (0.1 mol) were added to an electrolytic cell. )
After adding an electrolytic solution containing nitrobenzene and nitrobenzene (total volume II l), constant current electrolysis was performed in air at 1 mA/aj for 8 hours to synthesize a benzene polymer.
膜厚：３５μｍ、σ： ４．５ Ｓ／ ａｍ （成長直
後）。Film thickness: 35 μm, σ: 4.5 S/am (immediately after growth).
実施例６゜
実施例１と同じ電解槽に、ベンゼン（０，１モル）とＮ
ｉ Ｃｌ１ｚ（Ｐ Ｐ ｈｓ）ｚ （０，１モル）
及びＮａＡｓＦａ （０，１モル）とをジクロルメタ
ン（全容量Ｉｌ）に溶かした電解液を入れた後、空気中
で１０ｍＡ／ｃｄで０．５時間、定電流電解を行ってベ
ンゼン重合体を合成した。Example 6゜In the same electrolytic cell as in Example 1, benzene (0.1 mol) and N
i Cl1z(P P hs)z (0.1 mol)
After adding an electrolytic solution in which NaAsFa and NaAsFa (0.1 mol) were dissolved in dichloromethane (total volume Il), constant current electrolysis was performed in air at 10 mA/cd for 0.5 hours to synthesize a benzene polymer. .
膜厚：２３μｍ１σ： ３．２ Ｘ １０−３Ｓ／ ｃ
ｌｌ（成長直後）。Film thickness: 23μm 1σ: 3.2 x 10-3S/c
ll (immediately after growth).
実施例７゜
実施例１と同じ電解槽に、ジフェニル（０，１モル）と
Ｎ１Ｃｌ２（ＰＰｈｚ）ｚ （０，１モル）及びＢｕ
ａＮ−Ａｓ Ｆ＆ （０，１モル）をニトロベンゼン（
全容量１ｍりに溶かした電解液を入れた後、電流密度１
５ｍＡ／−で０．５時間、定電流電解を行ってベンゼン
重合体を合成した。Example 7゜In the same electrolytic cell as in Example 1, diphenyl (0.1 mol), N1Cl2(PPhz)z (0.1 mol) and Bu
aN-As F& (0.1 mol) to nitrobenzene (
After adding the dissolved electrolyte to a total capacity of 1 m, the current density is 1
Constant current electrolysis was performed at 5 mA/- for 0.5 hours to synthesize a benzene polymer.
膜厚：３５μｍ、σ： ２．２ｘｌ Ｏ−”Ｓ／ ｃｓ
（成長直後）。Film thickness: 35μm, σ: 2.2xl O-”S/cs
(immediately after growth).
各実施例で得られた膜は光沢のある均質な膜であった。The films obtained in each example were glossy and homogeneous.
比較例
実施例１においてＮ ｔ Ｃｌ ｚ（Ｐ Ｐ ｈ （ａ
ｌｌｙｌ）） ｔを除く以外は全く同様にして電解反応
を行った。Comparative Example In Example 1, N t Cl z (P P h (a
llyl)) An electrolytic reaction was carried out in exactly the same manner except that t was removed.
電解表面に黒褐色重合物の浮遊が見られるが膜は形成さ
れなかった。Although black-brown polymer particles were seen floating on the electrolyzed surface, no film was formed.
Claims (1)
ゼン重合体を製造する方法において、重合を遷移金属錯
体の存在下で行うことを特徴とするベンゼン重合体の製
造方法。1. A method for producing a benzene polymer by electrochemically polymerizing benzene or a derivative thereof, characterized in that the polymerization is carried out in the presence of a transition metal complex.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3819386A JPS62197421A (en) | 1986-02-25 | 1986-02-25 | Production of benzene polymer |
| DE19863617777 DE3617777A1 (en) | 1985-05-27 | 1986-05-27 | ORGANIC SECONDARY ELEMENT |
| US07/219,869 US4935319A (en) | 1985-05-27 | 1988-07-12 | Organic secondary battery |
| US07/510,877 US5089359A (en) | 1985-05-27 | 1990-04-18 | Organic secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3819386A JPS62197421A (en) | 1986-02-25 | 1986-02-25 | Production of benzene polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62197421A true JPS62197421A (en) | 1987-09-01 |
Family
ID=12518522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3819386A Pending JPS62197421A (en) | 1985-05-27 | 1986-02-25 | Production of benzene polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62197421A (en) |
-
1986
- 1986-02-25 JP JP3819386A patent/JPS62197421A/en active Pending
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