JPS5915932B2 - New selenium-containing polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel selenium-containing polymer useful as a semiconductor material and a method for producing the same.

j0 In recent years, with the increase in demand for electronic materials in various fields, the development of new semiconductor materials has become an important issue, and research on organic semiconductors in addition to inorganic semiconductors has become active. Until now, organic semiconductors have been known in which electron acceptors are added to conjugated double bond type -5 polymers such as polyacetylene and polyphenylene to impart properties as semiconductors. However, unlike general-purpose thermoplastic polymers, many of the polymers used as semiconductor materials do not melt even when heated and remain in a solid state.
Polyacetylene has the drawbacks of poor moldability and processability, as well as poor chemical and mechanical properties, as it thermally decomposes in the atmosphere, and polyacetylene has the drawback of being susceptible to the action of oxygen and being unstable in the air. However, none of them can be said to be of practical use. 35 The present inventors have overcome the drawbacks of conventional organic semiconductors and have developed an organic semiconductor with excellent chemical and mechanical properties, which has good moldability and processability, and is stable in the air. As a result of intensive research to develop semiconductors, the inventors discovered that a certain type of selenium-containing polymer is suitable for the purpose, and based on this knowledge, the present invention was accomplished.

That is, the present invention provides a polymer comprising repeating units represented by the general formula (n in the formula is an integer of 1 or 2).

The polymer of the present invention is a new substance that has not been described in any literature, and all of them are stable in air and are electrically insulating as they are, but they contain sulfur trioxide, boron trifluoride, antimony pentafluoride, By adding an electron acceptor such as arsenic pentafluoride or iodine, it has properties as a semiconductor.

Further, polyphenylene selenide in which n in the general formula (1) is 1 has a melting point of about 170 to 270°C and is excellent in moldability and processability.

On the other hand, polydiphenylene selenide in which n is 2 has no melting point but has good thermal stability and is suitable not only as a semiconductor material but also as a heat-resistant resin. The selenium-containing polymer of the present invention can be produced, for example, by reacting it with a dihalide-containing alkali metal selenide represented by the general formula (wherein X is a halogen atom and n has the same meaning as above). can be manufactured.

Examples of the dihalide represented by this general formula () include p-dibromobenzene, p-diiodobenzene, p-
-dichlorobenzene, p-difluorobenzene, 4,4
'-Dibromodiphenyl, 4,4'-diiododiphenyl, 4,4f-dichlorodiphenyl, 4,4'-difluorodiphenyl, etc., but also those with two different halogen atoms, For example, p-chlorobromobenzene, 4-chloro-4'-promodiphenyl, etc. can also be used.

Further, as the alkali metal selenide, for example, sodium selenide, potassium selenide, lithium selenide, etc. are used.

The reaction between the dihalide and the alkali metal selenide is advantageously carried out in an inert solvent and under an inert atmosphere.

Suitable inert solvents in this case include N-methyl-2-pyrrolidone, pyrrolidone, prolactam, and N-ethylcaprolactam. Further, as the inert atmosphere, nitrogen, argon, etc. are used, but a closed system such as a sealed tube can also be used. By performing the polymerization under an inert atmosphere in this way, it is possible to prevent the selenium compound produced during polymerization from reacting with oxygen to produce by-products. The polymerization reaction is usually carried out by heating to 100 to 200°C and is completed in 30 minutes to several tens of hours.

After completion of the polymerization, the reaction mixture is filtered as it is or after diluted with an appropriate organic solvent, and the desired product is recovered as a precipitate. Then, if necessary, it is washed with water, dilute hydrochloric acid, hydrochloric acid-acidic methanol, etc. to remove inorganic impurities that may be contained therein. Next, low molecular weight compounds are removed by washing with a hot organic solvent. The organic solvent at this time is appropriately selected from those capable of partially dissolving the polymer obtained immediately after the polymerization is completed. Examples of such substances include chloroform, methanol, ethanol, benzene, and toluene. In the above method, if an alkali metal sulfide is used instead of an alkali metal selenide, the corresponding polyphenylene sulfide and polydiphenylene sulfide can be obtained.

Next, the present invention will be explained in more detail with reference to Examples.Example 1 p-dibromobenzene 2,369 (10 mmol), N
-Methyl-2-pyrrolidone (15 ml) and sodium selenide (1.25 g (10 mmol)) were polymerized in a sealed tube at 180° C. for 18 hours.

The reaction product was poured into methanol to cause precipitation, and the precipitate was collected on a glass filter, washed with water, and then with methanol. Next, this was extracted overnight using a Sotsutasure extractor using loloform as a solvent to remove low molecular weight compounds. When the unextracted portion was dried, a gray-colored powdery polymer with a weight of 0.729 g was obtained. This polymer has a melting point of approximately 2
It was 00-2700C. The results of differential scanning calorimetry of this material under a nitrogen atmosphere are shown in FIG. 1, and the results of thermogravimetric analysis also under a nitrogen atmosphere are shown in FIG. From this, it can be seen that the weight residual rate at 500°C is 46%. Incidentally, the infrared absorption spectrum of this polymer is shown in FIG. Example 2 p-diiodobenzene 16.51 (50 mmol), N
70 ml of -methyl-2-pyrrolidone and 6.251 (50 mmol) of sodium selenide were polymerized in a sealed tube at 180 DEG C. for 16 hours.

The reaction product was poured into methanol to cause precipitation, and the precipitate was collected on a glass filter and washed with water and methanol. After stirring the precipitate in methanol acidified with hydrochloric acid, it was filtered and washed with water and methanol. Next, this was extracted overnight using a Soxle extractor using chloroform as a solvent to remove low-molecular compounds.

When the unextracted portion was dried, a yellow powdery polymer 2.339 was obtained. The melting point of this polymer is about 170~
The temperature was 240°C. The infrared absorption spectrum of this polymer was the same as that of the gray-colored powdered polymer obtained in Example 1. Example 34,4'-diiododiphenyl 8.1
29 (20 mmol), N-methylpyrrolidone 40ml
, sodium selenide 2.509 (20 mmol) was polymerized in a sealed tube at 180° C. for 10 hours.

The reaction product was poured into methanol to cause precipitation, and the precipitate was collected on a glass filter and washed with water and methanol. Next, this was extracted overnight using a Soxle extractor using chloroform as a solvent to remove low-molecular compounds. When the unextracted portion is dried, a brown powdery polymer 2
．． 599 was obtained. This polymer did not melt even at 300°C, and differential scanning calorimetry showed that no peak indicating melting was observed up to 500°C. The results of thermogravimetric analysis are shown in FIG. From now on, the weight residual rate at 500℃ is 64%
Therefore, the thermal stability was good. The infrared absorption spectrum of this polymer is shown in FIG. Reference Example The gray-green powdered polymer obtained in Example 1 was solidified using an infrared molding machine (Shimadzu Corporation) under a pressure of 8t0n/(1-JmoVf).The conductivity of the resulting pellet was measured. It was 8.3 x 10-13 Ω-1 (1771-1 or less) at room temperature.

When this pellet was exposed to gaseous sulfur trioxide in a glass container at room temperature, the conductivity increased to 1.5 x 10-7 ohm-1 cm-1 after about 5 hours.

When this pellet was similarly exposed to gaseous boron trifluoride, the conductivity was 3.4 x 10-8 Ω- after about 150 hours.
It became 1-1.

When this pellet was exposed to antimony pentafluoride vapor, the conductivity was 1.3 x 10-1 after about 1 hour at room temperature.
Ω-1CT11-3.2X10 after about 30 minutes at 150℃
-0Ω-1CTL-1.

[Brief explanation of drawings]

Figure 1 is a graph showing the results of differential scanning calorimetry of one example of the compound of the present invention, Figure 2 is a graph showing the results of thermogravimetric analysis, Figure 3 is its infrared absorption spectral diagram, and Figure 4 is the graph showing the results of thermogravimetric analysis. A graph showing the results of thermogravimetric analysis of another example, FIG. 5 is an infrared absorption spectrum diagram thereof.

Claims (1)

[Claims] 1. A polymer consisting of repeating units represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (n in the formula is an integer of 1 or 2). 2. It is characterized by reacting a dihalide represented by the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (in the formula, X is a halogen atom, n is an integer of 1 or 2) and an alkali metal selenide. , formula ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ (n in the formula has the same meaning as above) A method for producing a polymer consisting of repeating units shown in the following.