JPH0749470B2 - Method for producing electrolytically oxidized polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for electrolytically oxidatively polymerizing naphthalene compounds or benzoquinones, wherein the resulting electrolytically oxidative polymer is an electrode,
It can be used as a material for electrical or electrochemical fields such as semiconductors.

[Conventional technology]

Conventionally, some electrolytic polymerization of benzene etc. is proposed. For example, in U.S. Pat.
₃ (R is an aromatic compound, X is chlorine or bromine) is electrolyzed using a ternary complex compound, and in JP-A-60-238316, benzene is electrolyzed using a Friedel-Crafts catalyst to obtain polyphenylene. .

[Problems to be solved by the invention]

However, such a method is not always sufficient in terms of current efficiency and the like to be applied to compounds other than benzene.

The present inventor arrived at the present invention by conducting studies to obtain these electrolytically oxidized polymers from naphthalene compounds or benzoquinones by the electrolytic polymerization method.

[Means for solving problems]

That is, the gist of the present invention is a method for producing an electrolytic oxidation polymer, in which naphthalene or benzoquinone is electrolytically oxidatively polymerized in a solvent in the presence of a protonic acid or a Lewis acid.

Hereinafter, the present invention will be described in detail.

In the present invention, electrolytic oxidative polymerization is carried out in a solvent in the presence of a protic acid or a Lewis acid.

As the protonic acid or Lewis acid, boron trifluoride,
Preferable examples include antimony pentachloride, aluminum chloride, aluminum bromide, tin tetrachloride, iron chloride, trifluoromethanesulfonic acid, trifluoroacetic acid and the like. Among them, particularly preferable are boron trifluoride, antimony pentachloride and aluminum chloride. Is.

As the solvent, nitrobenzene, nitromethane, dichloromethane, acetonitrile, propylene carbonate,
Water, tetrahydrofuran, benzonitrile and the like can be mentioned, of which nitromethane, nitrobenzene and dichloromethane are particularly preferable.

As naphthalene, the following general formula (I) (In the formula, R ^{1 to} R ⁶ may be the same or different and each represents a hydrogen atom, a halogen, an alkyl group, an optionally substituted phenyl group or a phenoxy group.). Examples of halogen include chlorine, bromine, fluorine, etc.
The alkyl group has a carbon number of 1 to 1 such as methyl group and ethyl group.
There are ten. Examples of the group which may substitute the phenyl or phenoxy group include an alkyl or alkoxy group having 1 to 10 carbon atoms and halogen.

Specific examples of such naphthalenes include naphthalene and 1-
Fluoronaphthalene, 1-methylnaphthalene, 2,6-diethylnaphthalene, 1,4 diphenoxynaphthalene, 2-phenylnaphthalene, 2-isopropylnaphthalene, 1-
Examples thereof include chloronaphthalene and 2-phenoxynaphthalene, and of these, naphthalene is particularly preferable.

As the benzoquinones, the following general formula (II) (In the formula, R ^{7 to} R ¹⁰ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an optionally substituted phenyl group or a phenoxy group.
Further, R ⁷ and R ⁸ and R ⁹ and R ¹⁰ do not represent the above groups other than hydrogen at the same time. ) Is used. The halogen atom is chlorine, bromine, fluorine or the like, the alkyl group is a methyl group, an ethyl group or the like having 1 to 10 carbon atoms, and the alkoxy group is a methoxy group or an ethoxy group or the like having 1 to 10 carbon atoms. Can be mentioned. Examples of the group which may substitute the phenyl or phenoxy group include an alkyl or alkoxy group having 1 to 10 carbon atoms and a halogen atom.

Specifically as such benzoquinones, benzoquinone,
2-methylbenzoquinone, 2-methoxybenzoquinone,
Examples thereof include 2-phenoxybenzoquinone, 2-chlorobenzoquinone, 2-fluorobenzoquinone, and 2,5-dimethylbenzoquinone, and among these, a particularly preferable compound is benzoquinone.

The electrolytic oxidative polymerization is carried out in a usual electrolytic cell. The anode is preferably a platinum group metal such as platinum, palladium or ruthenium, and platinum is particularly preferred. The cathode is carbon, Nesa glass,
It is preferably selected from platinum group metals and the like. The operating conditions for electrolysis can be in a wide range. The temperature is from -10 ℃ to 100 ℃,
The temperature is preferably 0 to 50 ° C, more preferably 10 to 30 ° C.
The applied voltage may vary within a range of about 1 to 100 V, but it is possible to apply a voltage outside this range. The current density is also the density required to obtain the polymer, usually 0.005 amps / cm.
² or more apply. The electrolysis conditions are selected such that the optimum current efficiency is exhibited according to the composition of the polymerization solution. The time required for electrolytic polymerization is usually several minutes to several hours, although it varies depending on the degree of energization and the composition of the polymerization liquid.

The amount of naphthalene and benzoquinone in the electrolyte is 0.01mo
l / ~ 3mol /, the amount of protic acid, Lewis acid is 0.05mol /
~ 7mol / is usually applied.

Polynaphthalene and polybenzoquinone are produced on the anode of naphthalene and benzoquinone by electrolytic oxidation polymerization. It is also possible to adjust the film thickness of this polymerized film by prolonging the energization time. The obtained polymer is washed with water, dilute hydrochloric acid, methanol or the like, if necessary.

The polynaphthalene obtained by the method of the present invention is a novel polymer having a poly 1,4-naphthalene structure represented by the following general formula (III).

(In the formula, R ^{1 to} R ⁶ have the same meanings as those in the general formula (I).) The polybenzoquinones obtained by the method of the present invention are also novel compounds having a polybenzoquinone structure represented by the following general formula (IV). It is united.

(In the formula, R ^{7 to} R ¹⁰ have the same meanings as in the general formula (II).) [Effect of the Invention] According to the method of the present invention, naphthalene compounds and benzoquinones can be easily obtained with high electrolysis efficiency. Further, the obtained polynaphthalene and polybenzoquinone are useful as materials for electricity and electrochemical such as electrodes and semiconductors.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 1.73 g of p-benzoquinone and 10.67 g of anhydrous aluminum chloride
Dissolve 0.1 g of water in 75 ml of nitromethane and ventilate with nitrogen gas to deoxygenate. Two platinum plates (2 x 5 cm) were placed facing each other at 1 cm intervals, and electrolysis was performed at 2500 C at a set current of 50 mA. A black polymer thin film was formed on the anode and washed with water-methanol to obtain a polymer in a yield of 6%.

IR spectrum ν _{C = O} 1640,1620 cm ⁻¹ Elemental analysis value (theoretical value) C: 67.8 (67.9), H: 1.32 (1.8
8) confirmed the structure of polybenzoquinone.

The IR absorption spectrum of the obtained polybenzoquinone is shown in FIG.

Example 2 1.73 g of p-benzoquinone and 15 ml of boron trifluoride diethyl ether were dissolved in a nitrobenzene solution (65 ml).
Two platinum plates (2 × 5 cm) were placed facing each other at 1 cm intervals. Electrolysis was performed at a set potential of 1.8 V at 1.5 F / mol. A black polymer film was obtained on the anode. The membrane is washed with methanol, the yield is 0.
It was 15 g.

IR spectrum ν _{C = O} 1640,1620 cm ^-1 Elemental analysis value (theoretical value) C: 66.6 (67.9), H: 1.72 (1.8
8) Example 3 7.18 g of naphthalene, 10.67 g of anhydrous aluminum chloride and 0.1 of water
g is dissolved in 75 ml of nitromethane, and nitrogen gas is bubbled through to deoxygenate. Two platinum plates (2 × 5 cm) were placed facing each other at 1 cm intervals, and electrolysis was performed at 0.6 F / mol at a set current of 0.5 A. A brown polymer was formed on the anode and washed with water-methanol to obtain the polymer with a current efficiency of 37%.

The structure of polynaphthalene was confirmed from the IR spectrum ν _{C = C} 1620,1500,1420,1370 cm ⁻¹ δ _CH 820,760 cm ⁻¹ .

The IR absorption spectrum of the obtained polynaphthalene is shown in FIG.

Example 4 7.18 g of naphthalene and 15 ml of antimony pentachloride were dissolved in 65 ml of nitrobenzene. Add 1 platinum plate (2 x 5 cm) to this.
Installed face-to-face at an interval of cm, and set potential 2.0V (VS Ag / AgCl)
It was electrolyzed at 1 F / mol. A polymer was formed on the anode and 1.8 g was obtained after washing with water-methanol.

The IR spectrum ν _{C = C} 1620,1500,1420,1370 cm ⁻¹ δ _CH 820,760 cm ⁻¹ confirmed the polynaphthalene structure.

Example 5 3.59 g of naphthalene, 15 m of boron trifluoride diethyl ether
l was dissolved in 65 ml of nitromethane. Platinum plate (2 x 5
cm) 2 pieces were installed at 1 cm intervals. 6.5 F / m at constant potential of 200 mA
ol electrolyzed. A brown polymer was formed on the anode, and 0.51 g was obtained after washing with methanol.

IR spectrum ν _{C = C} 1620,1500,1420,1370cm ^-1 _HC 820,760cm ^-1

[Brief description of drawings]

FIG. 1 shows the IR absorption spectrum of the polybenzoquinone of Example 1, and FIG. 2 shows the IR absorption spectrum of the polynaphthalene of Example 3.

Claims (1)

[Claims] 1. A process for producing an electrooxidative polymer, which comprises subjecting naphthalene compounds or benzoquinones to electrooxidative polymerization in a solvent in the presence of a protic acid or a Lewis acid.