JPS629607B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing polyarylene vinylene. Since polyarylene vinylene is a conjugated aromatic polymer containing carbon-carbon double bonds, it is well known that it has useful properties such as heat resistance, electrical conductivity, and optical properties, and various attempts have been made to synthesize this material. being done. For example, (1) the use of the Wittig reaction, that is, the condensation reaction of bisphosphorane and dialdehyde; (2) Utilization of the Knoevenagel reaction, that is, the direct condensation reaction of active methyl groups with aldehydes H ₃ C−Ar−CH ₃ +OHC−Ar′−CHO →(−Ar−CH=CH−Ar′−CH ＝CH)− _o (3) Utilization of dehydrohalogenation reaction in which various strong bases (t-Buok, NaNH ₂ , NaH, etc.) act on bishalomethylarylene compounds X−CH ₂ −Ar−CH ₂ − Methods such as X→(-Ar-CH=CH) _-o are known. These methods are excellent synthetic methods and have high practical value, but for example, the use of the Wittzig reaction in (1) requires substituents that react with the ylide, such as amino groups, carbonyl groups, and hydroxyl groups. Since the compound cannot be synthesized and the product is a mixture of cis and trans isomers, cis-to-trans isomerization is required to improve oxidation stability, softening point, electrical conductivity, etc. is necessary. In the Knebenagel reaction (2), the reaction does not proceed unless the methyl group is activated by an electron-withdrawing group such as a nitro group or an amino group, and the range of raw materials is limited. In the dehydrohalogenation reaction (3), since the polymer contains an active halomethyl group, the selection of raw materials is limited because the polymer cannot contain an amino group or the like that reacts with the active halomethyl group. Each of them has drawbacks. Therefore, the present inventors conducted various studies for the purpose of solving the reaction problems of polyarylene vinylene and finding an excellent manufacturing method. As a result, we have discovered a new method for producing polyarylene vinylene that can be easily produced with good yield. The method for producing polyarylene vinylene of the present invention has the general formula: X-Ar-X [A] However, Ar is

【formula】

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【formula】

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【formula】

[Formula], Z ¹ is selected from the group consisting of -C= and -N=; Z ² is -O-, -S-,

[Formula] is selected from the group consisting of; G is -O-,

P is an integer selected from 0 and 1; X is selected from the same or different bromine or iodine; ) and the dihaloarylene compound represented by the general formula (However, R ₁ , R ₂ , R ₃ , and R ₄ are each one of hydrogen, methyl group, and ethyl group.) A divinyl arylene compound represented by By reacting in the presence of a hydrogen halide scavenger, the general formula (However, Ar, R ¹ , R ² , R ³ , R ⁴ are the same as above,
(n is an integer of 2 to 50) The object of the present invention is to easily produce polyarylene vinylene with good yield. This reaction usually 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 bicarbonate and sodium carbonate. Some specific examples of dihaloarylene compounds of general formula [A] that can be used in the present invention include P-dibromobenzene, m-dibromobenzene, P-diiodobenzene, 2,5-dibromopyridine, 1,4
-dibromonaphthalin, 1,5-dibromonaphthalin, 5,7-dibromoquinoline, 9,10-dibromoanthracene, 3,4-dibromothiophene, 3,4-dibromopyrrole, 3,4-dibromobiphenyl, 4. Some include 4'-dibromo-P-terphenyl and the like and mixtures thereof. In addition, some specific examples of divinylarylene compounds represented by the general formula [B] include: P-divinylbenzene, P-diisopropenylbenzene, m
- dipropenylbenzene, and analogs and mixtures thereof. In the method of the present invention, a dihaloarylene compound represented by the general formula [A] and a divinylarylene compound represented by the general formula [B] are heated at 75°C in the presence of, for example, palladium acetate, triarylphosphine, and a tertiary amine. The reaction is carried out at a temperature of ~150°C, and the reaction is completed in 1 to 50 hours. Triarylphosphines include triphenylphosphine, tri-O-tolylphosphine, tris(2,5-diisopropylphenyl)phosphine, tri-α-naphthylphosphine, tris(2,3,4,5- Tetramethylphenyl)phosphine, tris(2-methyl-5-t-butyl)
Examples include phosphine, tris(P-carbomethoxyphenyl)phosphine, and the use of tri-O-tolylphosphine and tris(2-methyl-5-t-butylphenyl)phosphine is particularly preferred. The triarylphosphoine used in the present invention is 0.5 to 10% per mole of palladium acetate.
Moles are appropriate. In addition, the amount of palladium acetate used is 0.5 to 4 mol% of the amount of divinylarylene used.
is appropriate. Tertiary amines are used as scavengers for generated hydrogen halides, but triethylamine, tri-
Commonly used amines such as n-butylamine, triamylamine, and tetramethylethylenediamine may be used, and the amount used is usually slightly in excess of the equivalent mole relative to the generated hydrogen halide. As the reaction solvent, common solvents such as N.
N-dimethylformamide, dimethylacetamide, toluene, xylene, chlorobenzene, O-
Dichlorobenzene, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,
Dimethyl sulfoxide, acetonitrile, etc. are used. Dihaloarylene [A] and divinylarylene [B] may each be a combination of two or more types. Both end groups of the polymer [C] obtained by the method of the present invention are usually hydrogen, bromine, or iodine, and in particular, the end group on the vinyl group side is usually hydrogen. The polymers are generally thermoplastics of excellent high temperature stability, and depending on the reactants chosen, some are soluble in solvents and can also be formed into films by casting processes. The method of the present invention can be used in a wider range of compounds than conventional methods, and by utilizing this reaction, it is also possible to produce polymers that were previously impossible to produce. The polymer produced by the method of the present invention has useful properties such as heat resistance, electrical conductivity, and optical properties like polymers produced by other methods, and can be used for any purpose. I can do it. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Example 1 1.21 parts of P-dibromobenzene (parts by weight, same hereinafter), 0.65 parts of P-divinylbenzene, tri-n-
Butylamine 1.95 parts, palladium acetate 0.022 parts,
A mixture consisting of 0.12 parts of tri-O-trisulfosphine and 2 parts of xylene was reacted at 120° C. for 5 hours with stirring under a nitrogen atmosphere. After the reaction, the resulting precipitate was thoroughly washed with methanol and toluene and dried to obtain 1.06 parts of a yellow polymer. The obtained polymer was insoluble in ordinary organic solvents, and was confirmed to be poly-paraphenylene vinylene from an infrared absorption spectrum. The infrared absorption spectrum is shown in FIG. It is unknown how bromine is bonded in the polymer, but assuming that one end of the polymer is a vinyl group and the other end is bromine, the molecular weight is 1140 from the quantitative value of bromine of 7%. n is calculated as 5. Example 2 1.14 parts of 1,4-dibromonaphthalene, 0.52 parts of P-divinylbenzene, tri-n-butylamine
A mixture consisting of 1.86 parts of palladium acetate, 0.018 parts of palladium acetate, 0.049 parts of tri-O-tolylphosphine, and 5 parts of N-methyl-2-pyrrolidone was reacted at 100° C. for 4 hours and 30 minutes with stirring under a nitrogen atmosphere. After the reaction, the reaction mixture was poured into methanol. Thoroughly wash the precipitate with methanol and toluene,
By drying, 1.07 parts of an orange polymer was obtained.
According to the infrared absorption spectrum of the obtained polymer,
CH out-of-plane bending absorption δtrans (CH=CH) of the trans-substituted vinyl group is confirmed at 952 cm ^-1 . When the n value was determined in the same manner as in Example 1, bromine was 8%;
At a molecular weight of 950, n is 3. Examples 3-7 Dihaloarylene and divinylarylene were polymerized under various conditions in the same manner as in Examples 1-2. Examples are shown in the table below.

【table】 [Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of the polymer of the present invention produced in Example 1.

Claims (1)

[Claims ^] 1 General formula and -N=; Z ² is selected from the group consisting of -O-, -S-, [Formula]; G is -O-,
P is an integer selected from 0 and 1; X is selected from the same or different bromines or iodines; ) and the dihaloarylene compound represented by the general formula (However, R ₁ , R ₂ , R ₃ , and R ₄ are each one of hydrogen, methyl group, and ethyl group.) A divinyl arylene compound represented by General formula, characterized in that the reaction is carried out in the presence of a hydrogen halide scavenger. (However, Ar, R ₁ , R ₂ , R ₃ , R ₄ are the same as above,
n is an integer of 2 to 50) A method for producing polyarylene vinylene. 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.