JPS61148235A - Production of polyvinylene chalcogenide - Google Patents

Abstract

PURPOSE:To obtain the titled chalcogenide having excellent heat resistance and useful as an organic polymer semiconductor, etc., by adding a specific chloride or a phase transfer catalyst to a reaction system, thereby remarkably increasing the shrinking and blackening temperature and the temperature to generate yellow liquid by the thermal decomposition. CONSTITUTION:The objective chalcogenide can be produced by adding (A) the chloride of a group IB metal (e.g. cuprous chloride) or (B) a phase transfer catalyst to a reaction system of (C) 1,2-dihalogenated ethylene and (B) an alkali metal chalcogenide. For example, the component C is the component of formula (X and X' are F, Cl, Br or I) (e.g. 1,2-dichloroethylene), and the component D is the compound of formula M2L (M is Na, K, Li, Rb or Cs; L is S or Se) (e.g. sodium sulfide anhydride).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing polyvinylene chalcogenide. The present invention also relates to a method for producing polyvinylene sulfide, which is a type of polyvinylene cargunide.

(Prior Art) Polyvinylene chalcogenide is a one-dimensional polymer containing a chalcogenide atom in its main chain, and polyvinylene sulfide is particularly one in which the chalcogenide atom is a sulfur atom. These chalcogenide-containing polymers have certain electrical and thermal properties in their structures, and are useful as organic polymer semiconductors or heat-resistant polymers.

The present inventors first developed a method for producing polyvinylene chalcogenide in which XHC=CHX', where X.

X' proposed a method of reacting F, CI, Br, and I with alkali metal chalcogenide (Japanese Patent Application No. 1983-
No. 60943, hereinafter referred to as Prior Application 1). In addition, the present inventors previously proposed a method of reacting 1,2-dichloroethylene with sodium sulfide as a method for producing polyvinylene sulfide (Japanese Patent Application No. 58-19821,
Patent Application No. 59-62157, hereinafter referred to as Prior Application 2. The above polymers have the disadvantage of low heat resistance. For example, shrinkage and blackening occur in polyvinyl obtained by the method of Prior Application No. 3.

Furthermore, when the temperature reaches 180°C, both polyvinylene sulfides undergo thermal decomposition and begin to release a yellow liquid.

As described above, it is necessary to further study the polymer obtained by the production method of the prior application in view of its low heat resistance.

(Means for Solving the Problems) Therefore, the present inventors conducted repeated research on a method for producing polyvinylene chalcogenide from 1,2-dihalogenated ethylene and alkali metal chalcogenide, and found that It was discovered that the heat resistance could be improved by adding a chloride of a group metal or a phase transfer catalyst, and based on this knowledge, the present invention was developed.

The present invention involves adding a Group IB metal chloride or a phase transfer catalyst to the reaction system of 1,2-dihalogenated ethylene and an alkali metal chalcogenide. As a compound, the structural formula % formula % (where x, x' are fluorine F, chlorine Ct, bromine B
r.

(represents either iodine), and these can be used in cis-type, trans-type isomers, or mixtures thereof. Preferably, the cis or trans form of 1,2-dichloroethylene is used. The alkali metal chalcogenide has the general formula M, L (where M is Nat K * Li + Rb + C
s, and L represents S or Se) is used. There may be two types of alkali metal chalcogenide, an anhydrous salt and a hydrated salt, and in order to obtain polyvinylene chalcogenide having a pure structure, it is preferable to use an anhydrous salt. More preferably, the anhydrous salt of sodium sulfide, Na2S, is used.

Here, as l,2-dihalogenated ethylene, 1
). Polyvinylene chalcogenide produced using 2-dichloroethylene and anhydrous sodium sulfide as the alkali metal chalcogenide is particularly known as polyvinylene sulfide.

: As the chlorides of group TR metals, cuprous chloride"',
Examples include CuC1, cupric chloride CuC72, and AgCj chloride, but preferably cuprous chloride CuC1 is used.

Examples of the phase transfer catalyst include benzyl IJ methylethylammonium chloride, tetra n-butylammonium bromide, benzyltributylammonium bromide, tetraethylammonium bromide, and tetramethylammonium iodide.

Quaternary ammonium salts such as tetraethylammonium bromide and tetra n-butylammonium iodide, or quaternary ammonium salts such as benzyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, methyltriphenylphosphonium bromide, and tributylhexadecylphosphonium bromide. class phosphonium salt, or 12-crown-4,15-crown-5,benzo-1
5-crown-5,18-crown-6, dibenzo-1
Cyclic polyethermines such as 8-crown-6, dicyclohexyl-18-crown-6, dibenzo-24-crown-8, dibenzopyridino-18-crown-6,
Alternatively, it is possible to use cyclic polyether sulfide or the like.

In the production method of the present invention, the presence of a solvent is preferred for the polymerization reaction, and dimethyl sulfoxide is preferred as the solvent.

Moreover, in the present invention, it is preferable to carry out the reaction at a temperature range of 10 to 60°C.

Although the reaction time is not particularly limited, the optimum reaction time is determined by balancing the stability of the product in the solvent, the reaction temperature, and the solubility of the raw materials in the reaction solvent. 10
In the temperature range of ~60°C, a reaction time of at least 1 hour is required.

The produced target polymer can be obtained as a precipitate by removing by-product alkali metal halides from the reaction solution by filtration and then pouring the filtrate into a large amount of methanol.

The heat resistance of the obtained polymer can be easily examined as follows. First, as the polymer is turned into powder, it thermally decomposes and a yellow to reddish-yellow liquid adheres to the capillary tube wall.

- (Effect of the invention) In polyvinylene/<A/phyto produced by the conventional production method, the temperature at which shrinkage and blackening occurs is 120 to 150°C, and the temperature at which yellow liquid is generated by thermal decomposition is 180°C. On the other hand, even with the same polyvinylene sulfide, when the catalyst of the present invention is added to the reaction system, the shrinkage/blackening temperature increases significantly, and the temperature at which yellow liquid is generated due to thermal decomposition also increases significantly. did it.

(Example) Analysis by gas chromatography/mass spectrometry revealed that the yellow liquid produced by thermal decomposition of polyvinylene sulfide was 1,4-dithiine. It is thought that the polyvinylene sulfide chain is cleaved by thermal decomposition, and a 6-membered ring dithiine is generated.

The polyvinylene sulfide produced by the present invention has a higher thermal decomposition initiation temperature and improved heat resistance than that produced by conventional methods.

,, ゛1 Example 1 ゛ The inside of an autoclave with a capacity of 1000 m / is replaced with argon gas and sulfurized) A mixed solution of IJium anhydrous salt 40.59 and salt chloride sulfoxide 500 Tut is dropped,
It was confirmed that it was a pure polyvinylene sulfide structure containing both anti-trans structures.

Pack conopolyvinylene sulfide into a capillary tube,
When a heating experiment was conducted, shrinkage started at 150 to 200°C, but no yellow liquid was observed due to thermal decomposition up to 250°C.

Example 2 The inside of a 50-capacity autoclave was replaced with argon gas, and 5 g of anhydrous sodium sulfide salt Na2S and 0.59 g of 18-crown-6 were put therein. After sealing the autoclave, a mixed solution of trans-1,2-dichloroethylene 2I and dimethyl sulfoxide 30d was added dropwise, and the mixture was heated to 96°C at 40°C.
Stir vigorously for an hour. When the reacted tear fluid was poured into 600 ml of methanol, a whitish brown precipitate was immediately formed. The yield was 086g.

The inside of an autoclave with a capacity of J150rnl was filled with argon gas λ1. Add 2 g of trans-1,2-dichloroethylene
A mixed solution of jl l' and dimethyl sulfoxide 301 was added dropwise, and the mixture was vigorously stirred at a reaction temperature of 40° C. for 92 hours. 60% of the reaction filtrate
When poured into 0 d of methanol, a whitish brown precipitate was immediately formed. Yield was 074g.

When a heating experiment was conducted on this polyvinylene sulfide, no generation of yellow liquid due to thermal decomposition was observed up to 220°C.

Example 4 - l〇 - The inside of an autoclave with a capacity of 300 mJ was replaced with argon gas, 30 g of anhydrous sodium sulfide and 24 g of cetyltrimethylammonium chloride were charged, and 712 g of trans-1,2-cycloethyl L' and dimethyl sulfoxide were added. Add 180 ml of the mixed solution dropwise and adjust the reaction temperature to 40°.
Stir vigorously for 95 hours at C. When the reaction filtrate was poured into methanol (4-e), a whitish brown precipitate was produced. The yield was 4.7g.

Volume * 50 ml autoclave with argon gas 1
8 g of sodium selenide Na25e and 0.8 g of cuprous chloride were added, and a mixed solution of 2 g of cis-1,2-dichloroethylene and 30 ml of dimethyl sulfoxide was added dropwise, and the mixture was heated at room temperature for 12 hours. Stir vigorously.

When reaction F solution was poured into 600ml of methanol,
A yellow brown precipitate formed. It was confirmed by IR spectrum measurement that it was a polyvinylene selenide structure.

When a heating experiment was conducted on this polyvinylene selenide, thermal decomposition did not occur up to 230C.

Example 6 The inside of an autoclave with a volume of 150 m was replaced with argon gas, sodium selenide Na25e89 and benzyltributylammonium bromide 045I were put therein, and 1.
A mixed solution of 12 g of a cis-trans mixture of 2-dibromoethylene and 30 g of dimethyl sulfoxide was added dropwise, and the mixture was vigorously stirred at room temperature for 24 hours. When the reaction P solution was poured into 600T1) methanol, a brown polyvinylene selenide precipitate was obtained.

I Procedural amendment 1, Indication of the case 1982 Patent Face No. 269662 2, Name of the invention Relationship to the case Patent applicant name Agency of Industrial Science and Technology Next Generation Industrial Technology Planning Miyake Telephone 501-
151) Extensions 4601-54, "Detailed Description of the Invention" column 5 of the specification to be amended, Contents of the amendment (1) Page 4 of the specification, lines 18-19 "As 1,2-dihalogenated ethylene, Use 1,2-dichloroethylene and delete ".

(2) At the end of page 4, “Using sodium sulfide anhydrous salt” was changed to “
Use sodium sulfide.''

(3) Page 8, lines 3 to 5 “However, the present invention
...I was able to rise. "However, according to the manufacturing method of the present invention, it was possible to significantly increase the shrinkage/blackening temperature and the temperature at which yellow liquid is generated due to thermal decomposition."
I am corrected.

that's all

Claims (1)

[Claims] (1) A method for producing polyvinylene chalcogenide, which comprises adding a chloride of a Group IB metal or a phase transfer catalyst to the reaction system of 1,2-dihalogenated ethylene and an alkali metal chalcogenide.