JPH0533260B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a novel polymer containing selenium or tellurium.

Since it was discovered that polymers such as polyacetylene and (SN) Many materials have been discovered to possess physical properties, and are attracting attention as new materials, and research is being actively conducted to put them into practical use.

[Conventional technology]

However, highly conductive polymers such as polyacetylene and (SN)x have drawbacks that hinder their practical application, such as insufficient stability and difficulty in producing raw materials. There are many.

[Problem that the invention seeks to solve]

The present inventors focused on Se and Te as constituent elements of conductive polymers, and as a result of intensive study on new polymers containing these elements, they discovered a new polymer that is easy to manufacture, and the present invention has been developed. Reached.

[Means for solving problems]

That is, the present invention provides the general formula (1) (-CH ₂ -) _o A _n - (1) [wherein A represents selenium or tellurium, m is an integer of 1 or 2, and n is 1 to 20 represents an integer. ] In producing an aliphatic selenium polymer or aliphatic tellurium polymer consisting of repeating units represented by the general formula (2) M _p A _n ...(2) (where M represents lithium or sodium and A represents selenium) or tellurium, p and m each represent an integer of 1 _{or 2} ) and a lithium or sodium compound represented by the general formula (3) X and Y represent chlorine, bromine, or iodine atoms, and n represents an integer from 1 to 20.

To explain the production method of the present invention in more detail, examples of methods for synthesizing the lithium or sodium compound of general formula (2) include the following methods.

(A) Te＋HOCH ₂ OSONa＋3NaOH→CH ₂ O＋
Na ₂ Te + Na ₂ SO ₃ +H ₂ O (B) mTe + 2LiB (CH ₂ CH ₃ ) ₃ H→Li ₂ Tem + B
(C ₂ H ₅ ) ₃ + H ₂ (m = 1, 2) (C) 2Na + mTe → Na ₂ Tem (m = 1, 2) In reaction (A), water was used as the solvent, and reactions (B) and (C) In this case, ethers such as tetrahydrofuran and dioxane, and organic solvents inert to the reaction such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are used. In either case, the reaction is carried out in an atmosphere of an inert gas such as nitrogen or argon at a temperature ranging from room temperature to the boiling point of the solvent.

In this way, a lithium or sodium compound of selenium or tellurium represented by the general formula (2) is obtained.

A solution of a halogen compound represented by general formula (3) is added dropwise to this reaction solution, and the reaction solution is stirred to react. Any organic solvent that is inert to the reaction may be used as the solvent for dissolving the halogen compound, but examples include ethers such as diethyl ether, tetrahydrofuran, and dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, Examples include polar solvents such as dimethylacetamide and N-methylpyrrolidone.

When the aliphatic selenium polymer or aliphatic tellurium polymer obtained in this way is produced as a precipitate, it is used as it is, and when it is dissolved in the reaction solution, the reaction solution is dissolved in a non-solvent for the polymer such as methanol. to form a precipitate, which is then separated by filtration. The separated polymer is purified by washing with a solvent or reprecipitation.

These polymers can be used in various applications as films or powders. When used as a film, it is preferable that n in the general formula (1) is 4 to 16 from the viewpoint of film forming properties.

〔Effect of the invention〕

As described above, according to the method of the present invention, Se, Te
A novel conductive polymer containing the following can be easily obtained. In addition to being a conductive polymer, the polymer is expected to be used as a material for optical disks because of its large color change due to thermal decomposition.

〔Example〕

This will be specifically explained below using examples.

Example 1 0.5g tellurium, 4g sodium hydroxymethanesulfinate, and 2.1g sodium hydroxide in 37ml
of water and heated under reflux for 15 minutes under a nitrogen atmosphere, and then cooled to precipitate white Na ₂ Te. next,
A solution of 1.2 g of 1,1-dibromodecane dissolved in 30 ml of dimethylformamide was added dropwise under a nitrogen atmosphere after the above reaction, and the resulting precipitate was allowed to react at room temperature for 6 hours, dissolved in carbon disulfide and poured into ether. Reprecipitation purification was performed.

The yield was 0.45g (81% yield).

Elemental analysis - C H as [-(CH ₂ -) ₁₀ Te-] Calculated value (%) 44.83 7.54 Actual value (%) 44.04 7.59 The infrared absorption spectrum of this polymer is shown in Figure 1.

Infrared absorption spectra were measured using the KBr method.

The main absorption peaks are 2910cm ^-1 , 2850cm ^-1 , 1450
cm ^-1 , 1140 cm ^-1 .

Example 2 0.9 g of sodium and 5.1 g of tellurium were added to 50 ml of dry dimethylformamide under a nitrogen atmosphere, heated to reflux to form Na ₂ Te ₂ , cooled to room temperature, and dissolved in 30 ml of dimethylformamide. 1,
6.0 g of 10-dibromedecane was added dropwise, and the reaction mixture was allowed to react at room temperature for 6 hours while stirring. The resulting precipitate was filtered and washed with dimethylformamide, water, and tetrahydrofuran in this order to obtain a polymer.

The yield was 4.9g (yield 59%).

Elemental analysis [(CH ₂ −) ₁₀ Te−Te−] C H Calculated value (%) 30.37 5.10 Actual value (%) 30.81 5.25 The infrared absorption spectrum of this polymer is shown in Figure 2.

The main absorption peaks are 2900cm ^-1 , 2830cm ^-1 , 1455
cm ^-1 , 1244cm ^-1 , 1180cm ^-1 , 1138cm ^-1 , and 719cm ^-1 .

Example 3 After adding 0.51 g (4 mmol) of tellurium into 8 ml of tetrahydrofuran, under a nitrogen atmosphere, 23.3 ml of a 0.45 M solution of lithium triethylborohydride in tetrahydrofuran was added, and after stirring for several minutes, an ultrasonic cleaner was used. When irradiated with ultrasonic waves, small bubbles were generated, and after about 2 hours, unreacted tellurium disappeared and a milky white suspension was formed. When a solution of 695 mg (4 mmol) of dibromomethane dissolved in 8 ml of tetrahydrofuran was added dropwise to this reaction solution, the mixture immediately became colored and a brown precipitate was precipitated.

The produced polymer was separated, dissolved in carbon disulfide, and purified twice by reprecipitation from diethyl ether to obtain a brown powder.

The yield was 18.1 mg (yield 3.2%).

Elemental analysis (-CH ₂ -Te-) C H Calculated value (%) 8.48 1.42 Actual value (%) 8.38 1.62 Example 4 After adding 0.32 g (4 mmol) of selenium to 8 ml of tetrahydrofuran, 0.45 9 ml of a tetrahydrofuran solution of lithium triethylborohydride (M) was added, and the mixture was irradiated with ultrasonic waves to react in the same manner as in Example 3, to obtain a dark red suspension of Li ₂ Se ₂ .

Add 600 mg of 1,10-dibromodecane to this reaction solution.
When a solution of (2 mmol) dissolved in 8 ml of tetrahydrofuran was added dropwise, the color turned clear orange. When this reaction solution was poured into methanol, a white-yellow precipitate was precipitated.

This precipitate was separated, dissolved in tetrahydrofuran, and reprecipitated from methanol to obtain a lemon-colored polymer.

The yield was 549.0 mg (yield 92.1%).

Elemental analysis value [(CH ₂ −) ₁₀ Se ₂ −] C H Calculated value (%) 40.30 6.76 Actual value (%) 40.70 6.87 The infrared absorption spectrum of this polymer is shown in Figure 3.

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectra of the polymers obtained in Example 1, FIG. 2 in Example 2, and FIG. 3 in Example 4.

Claims (1)

[Claims] 1 General formula (1) (-CH ₂ -) _o A- _n ...(1) [In the formula, A represents selenium or tellurium, m is an integer of 1 or 2, and n is 1 represents an integer from 12 to 12. ] In producing an aliphatic selenium polymer or aliphatic tellurium polymer consisting of repeating units represented by the general formula (2) M _p A _n ...(2) (where M represents lithium or sodium, A represents Represents selenium or tellurium, p and m
each represents an integer of 1 or 2. ) and the general formula (3) X(-CH ₂ -) _o Y...(3) (wherein, (Representing an integer of 12.) A method for producing an aliphatic selenium polymer or an aliphatic tellurium polymer, characterized by reacting a halogen compound represented by: