JPS621651B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyarylene ethynylene. Polyarylene and ethynylene are conjugated aromatic polymers containing carbon-carbon triple bonds, so they are heat resistant,
It is expected to have useful properties such as electrical conductivity and photoconductivity. However, a method for synthesizing such a polymer has not been known so far. Therefore, the present inventors conducted various studies in order to find an excellent manufacturing method. As a result, we have discovered a new method for producing polyarylene ethynylene that can be easily produced with good yield. The method for producing polyarylene/ethynylene of the present invention is characterized in that a haloethynylarylene compound represented by the general formula The object of the present invention is to easily produce polyarylene ethynylene represented by the general formula -(Ar-C≡C) _-o in good yield by carrying out the reaction described below. [However, Ar is

【formula】

##STR1## where R is selected from hydrogen and alkyl groups; X is bromine or iodine; n is a positive integer. ] Here, n in the above general formula represents the degree of polymerization, and is 2 to 50. This reaction typically requires a catalyst and a hydrogen halide scavenger. As a catalyst, a combination of a noble metal compound such as palladium acetate and a phosphorus compound such as triarylphosphine is suitable. Suitable hydrogen halide scavengers include amines such as secondary amines and tertiary amines, and basic salts such as sodium carbonate and sodium carbonate. Some specific examples of haloethynylarylene compounds represented by the general formula Ethynylcarbazole, 3-bromo-N-
Some include ethyl-6-ethynylcarbazole, 3-bromo-Nn-dodecyl-6-ethynylcarbazole and the like and mixtures thereof. In addition, in the manufacturing method of the present invention, the general formula (However, Ar' is the same as Ar above, and R ₁ and R ₂ are each one of hydrogen, methyl group, and ethyl group.) When reacted in the presence of a halobinylarylene compound represented by A conjugated aromatic polymer containing carbon double bonds and triple bonds, with the general formula

[Synthesis of P-bromo-1,2-dibromoethylbenzene]

Dissolve 10 parts of P-bromostyrene (manufactured by Aldrich) in 20 parts of chloroform, and then dissolve bromine in 10 parts of chloroform at 0 to 4°C.
A solution containing 9.4 parts was added dropwise. After reacting at the same temperature for 30 minutes, chloroform and unreacted bromine were distilled off to obtain 17.9 parts of P-bromo-1,2-dibromoethylbenzene. [Synthesis of P-bromo-phenylacetylene] A solution in which 4.1 parts of metallic potassium was added to 250 parts of t-butanol was heated to reflux, and 17.9 parts of P-bromo-1,2-dibromoethylbenzene was added thereto. Ta. After reacting for 1 hour, the reaction mixture was poured into 1000 ml of ice water, followed by addition of dichloromethane to extract the product. P-bromo-phenylacetylene 7.39 was obtained by distilling off dichloromethane and sublimating the residue at 60-80°C under reduced pressure (2 mmHg).
I got the department. (Melting point 63.4°C) [Synthesis of polymer] 1.09 parts of P-bromo-phenylacetylene, 1.02 parts of piperidine, 0.013 parts of palladium acetate, tri-
A mixture consisting of 0.03 parts of 0-tolylphosphine and 4 parts of xylene was reacted at 100°C for 5 hours. A solid was precipitated by pouring the reaction mixture into methanol. The obtained solid was washed with xylene and methanol and dried to obtain 0.56 part of a yellow polymer. In the IR chart of a polymer, only a small absorption of ν(C≡H) due to the polymer terminal is observed, and the absorption based on ν(C≡C) is observed at 2200 cm ^-1 .

[Synthesis of N-ethyl-3-bromo-6-formylcarbazole]

22.33 parts of N-ethyl-3-formylcarbazole (manufactured by Aldrich) was dissolved in 170 parts of acetic acid, and 16.5 parts of bromine was added dropwise while stirring. After reacting for 10 minutes, the reaction product was poured into ice water, and the precipitate was thoroughly washed with water and recrystallized from ethanol to obtain 26.0 parts of N-ethyl-3-bromo-6-formylcarbazole (yield) in the form of white needle-like crystals. rate of 86%). [Synthesis of 3-bromo-N-ethyl-6-vinyl-carbazole] Add 4.5 parts of dry dimethyl sulfoxide to 0.26 parts of sodium hydride (50%) under a nitrogen atmosphere and stir until the generation of hydrogen gas stops at 75°C. heated to. After cooling in an ice and water bath, 8.89 parts of methyltriphenylphosphonium iodide powder was added. After stirring the resulting red solution at room temperature for 10 minutes, 6.04 parts of N-ethyl-3-bromo-6-formylcarbazole dissolved in dimethylsulfoxide were added dropwise. 90 at 60℃
After stirring for a minute, the reaction mixture was poured into ice water, and the precipitated solids were thoroughly washed with water and dried. The obtained solid was dissolved in hexane, the hexane was distilled off from the hexane-soluble fraction, and the residue was recrystallized from ethanol to obtain pale yellow crystals of 3-bromo-
5.26 parts of N-ethyl-6-vinyl-carbazole (yield 88%) was obtained. (Melting point 95°C) [Synthesis of 3-bromo-N-ethyl-6-ethynyl-carbazole] After dissolving 3.38 parts of 3-bromo-N-ethyl-6-vinyl-carbazole in 20 parts of chloroform, the solution was heated to 0°C with stirring. 5.94 parts of bromine was added dropwise.
By distilling off chloroform and unreacted bromine, 5.18 parts of 3-bromo-6-dibromoethyl-N-ethylcarbazole was obtained. Metallic potassium 1.48 in 180 parts of n-butanol
Heat the solution to reflux and add 3 parts to it.
-Bromo-6-dibromoethyl-N-ethylcarbazole (5.18 parts) was added dropwise little by little. After dripping, 1
After reacting for an hour, the reaction mixture was poured into ice water. By collecting the precipitated solid and drying it, 3-bromo-N-ethyl-6-ethynyl-
2.75 parts of carbazole were obtained. [Synthesis of polymer] 1.00 parts of 3-bromo-N-ethyl-6-ethynyl-carbazole, 0.08 parts of palladium acetate, tri-
A mixture consisting of 0.021 parts of 0-tolylphosphine, 1.26 parts of tri-n-butylamine, and 6 parts of dimethylformamide was reacted at 50°C for 10 hours. A solid was precipitated by pouring the reaction mixture into methanol. The obtained solid was washed with toluene and methanol and dried to obtain 0.70 part of a polymer having the following structural formula. When n was determined in the same manner as in Example 1, it was 15. The IR chart is shown in Figure 2. Example 3 [3-bromo-N-n-dodecyl-6-vinyl-
Synthesis of carbazole] 3-bromo-N-n- was synthesized according to the method of Example 2, except that N-n-dodecyl-3-formylcarbazole was used instead of N-ethyl-3-formylcarbazole. dodecyl-6-vinyl-
Carbazole was obtained. [Synthesis of polymer] 3-bromo-N-n-dodecyl-6-vinyl-
A mixture consisting of 0.88 parts of carbazole, 0.36 parts of P-bromo-phenylacetylene obtained in Example 1, 0.024 parts of tri-0-tolylphosphine, 0.009 parts of palladium acetate, 0.51 parts of piperidine, and 4 parts of xylene was added to Polymerization was carried out according to the method to obtain 0.22 parts of polymer. In the IR spectrum of a polymer, ν(C≡
C) absorption based on is observed at 2200 cm ^-1 ;
And absorption based on CH out-of-plane bending absorption attached to the trans double bond is observed at 960 cm ^-1 , indicating the formation of a polymer having the following structural formula. The IR chart is shown in Figure 3.

[Brief explanation of the drawing]

Figures 1 to 3 are Examples 1 to 3, respectively.
1 is an IR chart of the polymer of the present invention produced by.

Claims (1)

[Claims] 1. A haloethynyl arylene compound represented by the general formula A method for producing polyarylene ethynylene represented by the general formula -(Ar-C≡C) _-o , characterized by: [However, Ar is represented by [Formula] [Formula], R is selected from hydrogen and an alkyl group; X is bromine or iodine; n is an integer from 2 to 50. ] 2 The hydrogen halide scavenger is a secondary amine or 3
2. The method according to claim 1, wherein the amine is a grade amine.