JPS6348312A - Production of polyacetylene - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as an electro-conductive material, a solar battery material, an electrode material or the like easily by a simple operation, by polymerizing acetylene in the presence of a cuprous halide and a specified compound. CONSTITUTION:Acetylene (A) is polymerized at $70-100 deg.C, preferably, 0-65 deg.C in a solvent (e.g., tetrahydrofuran) in the presence of 0.05-10mol, preferably, 0.1-5mol, per mol of acetylene, of a cuprous halide (e.g., cuprous chloride) as a catalyst and 0.10-50mol, preferably, 0.50-5mol, per mol of acetylene, of a 1,8-diazabicyclo[5,4,0]undec-1-ene (C) of formula I as an additive to obtain a polyacetylene having 2-30 repeating units of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel method for producing polyacetylene. More specifically, the present invention provides a material that is useful as an electrically conductive material, a solar cell material, an electrode, etc.
The present invention relates to an industrially advantageous method for producing polyacetylene having repeating units represented by C+ directly from acetylene using simple operations.

[Conventional technology]

In recent years, research has been actively conducted on ferroelectric polymer materials as one type of functional polymer materials, and among these, acetylene-based polymer compounds are attracting particular attention.

This acetylene-based polymer compound has semiconductor properties in terms of electrical conductivity, but by doping it with an electron donor or electron acceptor, the electrical conductivity can be dramatically improved. As a molecular material, it is expected to be applied to, for example, solar cells, lightweight storage batteries for automobiles, electrodes, sensors, and photoelectric conversion elements.

Conventionally, the acetylene-based polymer compounds include, for example, acetylene, 1,3-butadiyne or its derivatives, 2
．． Those using diacetylene compounds such as 4-hexadiyne or its derivatives, 3,5-octadiyne or its derivatives as raw materials are known, and among these, as polymer compounds using acetylene as raw materials, formulas 4C, ,C+
So-called poly(acetylene) having a repeating unit represented by the formula and polyacetylene having a repeating unit represented by the formula -+C2C← are known.

By the way, poly(acetylene) having the above repeating unit +CH=CH+ can be produced relatively easily by polymerizing acetylene in the presence of, for example, a Chi7'ler-Natsuta catalyst, but the repeating unit - Polyacetylene having +CmiC+ has conventionally been produced by a complicated multi-step process as shown below.

Na, liquid ammonia ()IcH0]! H
CmiCHNaC=CNa-(1)(II)0Ch-HOCH2CmiCCHzOHCICHzC5CCH,
CI-(III) (TV) NaN
Hz (IC)to) xNa-(C
E(JzNa l1ocllz4cA
DzclIzotl(V)
(Vl) SOZCI
NaNHzCICHz4C=C+2CHzCI
Na4CzC+zNa(■)
(■) -----Na 4C=Ch Na
II-(C=ChH(IX)
(X) That is, first, acetylene (1) is reacted with sodium metal in liquid ammonia to obtain sodium acetylide (n), and then metaformaldehyde is reacted with this to obtain l,4-dihydroxy-2-butyne ( III
), then this 1°4-dihydroxy-2-butyne (III) was induced to 1,4-dichloro-2-butyne (IV) by the action of thionyl chloride, and then sodium amide was reacted with it to form sodium Acetylide (V) is obtained. Furthermore, by sequentially repeating the steps of reacting metaformaldehyde, thionyl chloride, and sodium amide, sodium polyacetylide (Vl) is obtained, which is then reacted with acid to lead to polyacetylene (X).

However, this method for producing polyacetylene involves highly dangerous reactions and requires a large number of complicated steps, making it particularly difficult to produce polyacetylene with a high polymer content, and it is difficult to produce industrially produced polyacetylene. No, no.

[Problem that the invention seeks to solve]

The present invention aims to improve the drawbacks of such conventional polyacetylene production methods and to provide an industrial method that can produce polyacetylene directly from acetylene with simple operations without involving dangerous reactions. That is.

[Means for solving problems]

As a result of extensive research to achieve the above object, the present inventors discovered that acetylene was polymerized in the presence of cuprous halides and 1°8-diazabicyclo(5,4,0)unde-7-cene. The inventors have discovered that the object can be achieved by doing the following, and have completed the present invention based on this knowledge.

That is, the present invention provides cuprous halides and 1.8-
The present invention provides a method for producing polyacetylene having a repeating unit represented by the formula, which comprises polymerizing acetylene in the presence of diazabicyclo(5,4,0]unde-7-cene.

The present invention will be explained in detail below.

In the method of the present invention, cuprous halide is used as a catalyst in the polymerization reaction of acetylene, and 1,8-diazabicyclo(5,4,0)unde-7-cene (hereinafter referred to as
(abbreviated as DBU) is used. Examples of the cuprous halides include cuprous fluoride, cuprous chloride, cuprous bromide, and cuprous iodide, among which cuprous chloride is particularly preferred. The amount of the halogenated compound used is:
The amount is preferably selected from 0.05 to 10 mol, more preferably from 0.1 to 5 mol per mol of acetylene.

On the other hand, DBU is an ultra-basic substance having a structure represented by the formula and has extremely basic properties, has extremely excellent catalytic ability, and has the property of being soluble in most solvents.

The amount of DBU added is preferably 0.10 to 50 mol, more preferably 0.50 to 5 mol, per mol of acetylene.
Selected within the molar range.

The acetylene polymerization reaction in the method of the present invention is usually carried out in a solvent. Examples of this solvent include ethers such as tetrahydrofuran, dioxane, diethyl ether, and diisopropyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene;
Examples include aliphatic hydrocarbons such as n-hexane, alicyclic hydrocarbons such as cyclohexane, and among these, tetrahydrofuran is particularly preferred.

The reaction temperature is usually -70 to 100°C, preferably 0 to 65°C.
The reaction pressure is not particularly limited, and the reaction may be carried out under normal pressure or under increased pressure, but when the reaction is carried out under increased pressure, The pressure is below 50 kg/ci-G, preferably 5
kg/cIA-G or less is desirable. Furthermore, the reaction time depends on the type and amount of cuprous halide used, the amount of DBU used, the type of solvent, the reaction temperature, etc., but is usually 0.
．． It is about 5 to 48 hours, preferably about 4 to 20 hours.

The acetylene polymerization reaction in the method of the present invention may be carried out in the presence of air or, if desired, in an inert gas atmosphere such as nitrogen or argon, but it is preferably carried out in the presence of air.

Next, to explain one example of a preferred embodiment of the present invention, first, the required amount of cuprous halide powder and DBU are added to a suitable solvent, and after stirring thoroughly in the presence of air, A required amount of acetylene gas is introduced, and a polymerization reaction is carried out at a predetermined temperature for a predetermined time. At this time, the acetylene gas may be introduced at once, or may be introduced in multiple steps if desired. After the reaction is completed, the reaction product is isolated by means such as filtration, and then thoroughly washed with an acidic aqueous solution such as hydrochloric acid or sulfuric acid, followed by water, and dried to obtain the desired polyacetylene.

The polyacetylene obtained in this way is 2÷CmiC+
It has a repeating unit represented by, and the number of repeating units is usually in the range of 2 to 30.

According to the method of the present invention, polyacetylene can be directly produced from acetylene with simple operations, and the polyacetylene obtained can contain, for example, iodine, bromine, chlorine, arsenic pentafluoride, antimony pentafluoride, sulfur trioxide, Electron-accepting compounds such as perchlorate, or lithium, sodium,
By doping with an electron-donating compound such as potassium, it exhibits high electrical conductivity, so it can be used as a conductive polymer material, such as solar cells, lightweight storage batteries for automobiles,
It is expected to be applied to electrodes, sensors, photoelectric conversion elements, etc.

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

Example 1 50ml of tetrahydrofuran in a 200ml flask
and 5 mm of cuprous chloride powder.

Add l and j! , fA, then DBU40mm.

After stirring for 1 hour in the presence of air, the mixture was heated to 25°C.
While maintaining the temperature, add 300 cc of acetylene gas to 4
The mixture was introduced over a period of time, and further stirred at the same temperature for 1 hour.

Next, add the remaining 300 cc of acetylene gas to 25°C.
After 4 hours of introduction while maintaining the temperature at 436 mg of salt was obtained. This substance was identified by infrared absorption spectrum. The infrared absorption spectrum is shown in the attached drawing. Note that the reaction takes place in the presence of air.
It was carried out at normal pressure. In addition, DBU of the obtained polyacetylene
There was no solvent to dissolve the salt, so it was not possible to measure its molecular weight.

Example 2 Example 1 except that the first and second acetylene introduction times were each 2 hours.
Exactly the same operation as above was performed to obtain 421 mg of DBU salt of polyacetylene as a black powder.

Example 3 The same operation as in Example 1 was carried out except that the first and second acetylene introduction times were each 0.5 hours, and black powder polyacetylene DBU salt 30- 7 mg was obtained.

〔Effect of the invention〕

The method for producing polyacetylene of the present invention is a method of polymerizing acetylene in the presence of cuprous halide and DBU, and is simple and does not require a large number of complicated steps involving dangerous reactions unlike the conventional technology. Polyacetylene can be easily produced directly from acetylene by simple operations, and it can be said to be a method of extremely high industrial value.

[Brief explanation of drawings]

The figure is a red absorption spectrum chart of an example of polyacetylene obtained by the method of the present invention.

Claims (1)

[Claims] 1. Cuprous halide and 1,8-diazabicyclo [
5,4,0] A method for producing polyacetylene having a repeating unit represented by the formula -(C≡C)-, which comprises polymerizing acetylene in the presence of unde-7-cene.