JPS5821420A - Conjugated alternating copolymer - Google Patents

Abstract

PURPOSE:To obtain a linear conjugated alternating copolymer having improved thermal stability and moldability, by reacting a diethynyl heteocyclic compound with a dihalogeno heterocyclic aromatic compound in the presence of an amine and a specific catalyst. CONSTITUTION:(A) A diethynyl heterocyclic aromatic compound of formulaI(Ar is heterocyclic aromatic ring), e.g. 2,6-diethynylpyridine, is reacted with (D) a dihalogeno heterocyclic aromatic compound of formula II (X is halogen), e.g. 2,3-dihalogenothiophene, in the presence of (B) an amine and (C) a palladium compound, preferably palladium acetate, or a copper compound, preferably cuprous chloride, as a catalyst, preferably at 50-120 deg.C for 1-5hr, to give the aimed copolymer having repeating units of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a linear conjugated alternating copolymer and a method for producing the same.

Conventionally, as a polymer consisting of a -C=C-CmiC- group and an aromatic ring, fj IJ (jethinylbenzene), which is a combination of meta and para, has been known (J.

(such as a ring) has been reported (Polym@rPr
vprintg, Japan, vol. 30, AI, 1
60 pages (1981)].

However, the former /I (para-jethynylbenzene) undergoes thermal decomposition at 100°C, and the heat resistance of poly(metathynylbenzene) is lower than that of the raw material meta-jethynylbenzene. On the other hand, since it is difficult to synthesize highly pure meta-jethynylbenzene, /Li(meta-jethynylbenzene) thermally decomposes at 200 °C (J, Ory, Chew. 25, p. 637 (1960)].Also, in the latter (K■→C==C-R-CmiC+ type polymer (R is as above), the raw material Highly pure para
Jetynylbenzene is difficult to synthesize, and although it has better heat resistance than poly(jethinylbenzene), it lacks moldability because it is insoluble in organic solvents.

An object of the present invention is to provide a linear conjugated alternating copolymer having alternating 105C groups and heteroaromatic rings, which exhibits excellent thermal stability and good moldability.

According to the invention, general formula I -Ar-C! ! IC-Ar'-C=C-
A linear conjugated alternating polymer having a repeating structural unit represented by I (where Ar and A r / are the same or different heteroaromatic rings) is provided.

Further, according to the present invention, a jetynyl heteroaromatic ring compound represented by the following general formula (1) HC=C-Ar-C=CH II (wherein Ar is a heteroaromatic ring) is treated with a palladized adduct and copper in the presence of an amine. Under a compound catalyst, the following formula ■
r' is a heteroaromatic ring that is the same as or different from Ar, and X is herogone. -CmC-1(
A method for producing a linear conjugated alternating copolymer having a repeating structural unit represented by (where Ar and Ar' are as above) (
) will be provided.

Further in accordance with the present invention, the following general formula ■ X'MgC m C - A'r - C = g CM
gX' N (where Ar is a heteroaromatic ring, x' is I
・The digrignard reagent represented by
'-XWI (wherein Ar' is a heteroaromatic ring that is the same as or different from the above Ar,
X is the same or different from X')
General formula ■-Ar-Cg+=C-Ar'-C
A method 0) for producing a linear conjugated alternating copolymer having a repeating structural unit represented by mC-I (where Ar and Ar' are as described above) is provided.

Next, the present invention will be explained in detail.

The heteroaromatic ring represented by Ar and Ar' above refers to a heterocycle having aromaticity, such as a thiophene ring,
Examples include a pyridine ring, a furan ring, and a pyrrole ring.

Examples of the jetynyl heteroaromatic ring compound used in the production method (4) of the present invention include 2,5-diethynyltheofene, 2,6-jethynylpyridine, 2,5-jethynylfuran, and 2.

Examples include 5-jethinylvirol.

These jetinyl heteroaromatic compounds, such as 2.5-
Jetinylthio 7-unit is 2.

It is produced by reacting 5-dihalo-noteophene with trimethylsilylacetylene in the presence of an amine under the catalyst of a palladium compound and a copper compound, and further desilylating the reaction product with a metal halide (as described by the present inventors). (Refer to Japanese Patent No. 56-29379).

In addition, 2,6-jethinylpyridine can be prepared by known methods, for example,
2.6-Sihalognoviridine and trimethylsilylacetylene are reacted in an amine in the presence of a catalytic amount of bis(triphenylphosphine)dichloropalladium (2) and cupric iodide, and then the 2,6- It can be produced by treating bis(trimethylsilylethynyl)pyridine with a dilute aqueous potassium hydroxide solution in methanol at room temperature (8yi+th*sl m, 6
27 pages (198 Kui)].

The digrinard reagent used in the production method (B) of the present invention generally combines the jetinyl heteroaromatic compound with RM
' (R is an alkyl group, X' is the same as above) and a Grignard reagent represented by a solvent, such as diethyl ether,
It can be obtained by reaction in an ether such as tetrahydro7rane or dibutyl ether.

Further, as the dihalo heteroaromatic ring compound used in the production method (4) or (B) of the present invention, for example, 2.3-1
2.4-53,4- and 2,5-dihalonoteophene, 2.3-12.4-. 2, 5-, 2.6-53.4
- and 3,5-dihalo-r-noviridine, and the like.

Examples of the amine in the production method (4) of the present invention include primary amines such as methylamine, ethylamine, hexylamine, aniline, benzylamine, dimethylamine, diethylamine, methylethylamine, N-methylaniline, piperidine, etc. ! Secondary amine, trimethylamine, triethylamine, N, N-dimethylachiline, benzyldimethylamine, N, N, N',
Examples include @tertiary amines such as N'-tetramethylethylenediamine, and any amine that forms ammonium I-ride in the reaction process of the production method according to the present invention can be used. These amines are jetynyl heteroaromatic compounds 1
It is preferable to use it in a ratio of 5 moles or more per mole.

As the palladium compound which is the catalyst used in the production method (4) of the present invention, for example, Pd (PR's)
n (R' represents an alkyl group, phenyl group or aralkyl group, the same applies hereinafter), Pd (PR'5)tXt(X
indicates halogen. (Similarly below), Pd (AsR'l)t X@% Pd (NR'
Compounds represented by i)t The amount of the palladium compound catalyst to be used is preferably about 0.001 to 0.02 mol per 1 mol of the jetynyl heteroaromatic cycloadduct or digrinard reagent.

Examples of the copper compound which is a catalyst used in the production method (4) of the present invention include monovalent steel such as cuprous chloride, cuprous bromide, cuprous iodide, cuprous oxide, and hexaanide steel. Among these copper compounds, cuprous iodide and cuprous chloride are preferably used. The amount of the copper compound to be used is preferably about 0.001 to 0.01 mol per 1 mol of the jetynyl heteroaromatic compound.

The phosphorous component which is the catalyst used in the production method (B) of the present invention includes triphenylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, triamylphosphine,
Examples include dimefk phenylphosphine, methyldiphenylphosphine, and tris(dimethylamino)phosphine.
When IJN is contained, there is no need to use a phosphorus compound separately. When a phosphorus compound is used, the amount used is preferably 2 to 5 mol per 1 mol of the palladium compound catalyst.

Next, an example of the production method (4) of the present invention will be described. First, a jetynyl heteroaromatic compound, an equimolar amount of a dihalo-r-no-heteroaromatic ring compound, and 5 moles or more of an amine are dissolved in a solvent. Examples of the solvent include hydrocarbons, ethers, amines, alcohols, ketones, esters, nitro compounds 7'c, etc., and are not particularly limited, but depending on the molecular weight of the linear conjugated alternating copolymer to be produced. depends on its solubility, and in order to produce high molecular weight linear conjugated alternating copolymers, nitrobenzene, pyridine,
Preference is given to using solvents of fertile compounds such as aniline, N-methylpyrrolidone, N,N-dimethylformamide, hexamethylphosphoryltriade. Next, a palladium compound and a copper compound as catalysts are added to this solution and stirred.

A suitable reaction temperature is 50°C to 120°C, and a suitable reaction time is 1 to 5 hours.

After cooling the reaction solution, the solution is concentrated under reduced pressure, washed with an aqueous chlormonic acid solution to remove ammonium halide and catalyst residue, and then washed with a basic solution, such as a methanol solution of alkali wire mesh hydroxide, to give a blackish brown color. The linear conjugated alternating copolymer of the present invention is obtained as a powder.

Furthermore, the manufacturing method of the present invention (an example of odor is shown below).

First, the digrignard reagent and equimolar dihalo r)
A heteroaromatic compound is dissolved in a solvent such as ether.

Next, a palladium compound and a phosphorus compound as catalysts are added to this solution and stirred.

The appropriate reaction temperature is 40°C to 140°C, and the appropriate reaction time is 2 to 5 hours. The linear conjugated alternating copolymer of the present invention can be obtained as a blackish brown powder by preparing a diluted aqueous solution, removing catalyst residues, etc., and then washing with a basic solution, for example, a methanol solution of an alkali metal hydroxide. .

The terminal end of the polymer chain of the linear conjugated alternating copolymer obtained by the production method (4) or (B) of the present invention is usually hydrogen or halodane. In addition, polymerization [n is not particularly limited, but it is usually produced as a value of about 10 to 500, and it is easy to produce a value of about 'ritc-10 to 300.

The structure of the linear conjugated alternating copolymer of the present invention is mainly in the infrared (
IR) spectrum. That is, the absorption derived from the C═CH group of the jetinyl heteroaromatic ring of the raw material has disappeared, and the absorption based on the C═C bond is 60 to 101.
00c"" is shifted to the higher wavenumber side, and there is slight absorption in the aura aromatic ring constituting the linear conjugated alternating copolymer. The structure of the alternating copolymer was determined.

The linear conjugated alternating polymer of the present invention thus obtained has superior heat resistance compared to Bori (jethinylbenzene) K. That is, while poly(jethinylbenzene) thermally decomposes at temperatures below 200°C, the linear conjugated alternating copolymer of the present invention does not thermally decompose even at 300°C and is stable.

While the polymer is insoluble in organic solvents, the linear conjugated alternating copolymer of the present invention can be used, for example, in chloroform, toluene, THF%N, N-dimethylformamide, N-methylpyrrolidone, pyridine, aniline, hexamethyl It is soluble in organic solvents and media such as phosphoryltriamide and N,N-dimethylsulfoxide. Therefore, the linear conjugated alternating copolymer of the present invention can be easily molded by casting or other methods after dissolving it in a solvent. In addition, the linear conjugated alternating copolymer of the present invention can be used for organic semiconductor materials and organic conductive materials having various conductivity changes by controlling the degree of doping with various dopants such as electron-donating compounds or electron-withdrawing compounds. Becomes a material.

For example, without doping with sulfuric acid, the conductivity can be increased by up to 8 orders of magnitude or more.

As mentioned above, the linear conjugated alternating copolymer of the present invention is an organic semiconductor material with excellent heat resistance and moldability.
It is useful as an organic conductive material.

The present invention will be further explained by examples.

The degree of polymerization of the linear conjugated alternating copolymer in Example (in
Polystyrene-equivalent number average molecular weight (rn) f of linear conjugated alternating copolymer measured in N-methylpyrrolidone solvent using Wat@rs high-temperature high-speed r-permeation chromatogram (4 del 1500 GPC/ALC) Considering the structure of the linear conjugated alternating copolymer and the bulkiness of the linear conjugated alternating copolymer in the solution, Q linear conjugated alternating copolymer/Q/Restyrene- 〇、
It was calculated from the number average molecular weight (r') obtained by adopting No. 25.

Example 1 (1) 2.5-diethylene thiophene/was prepared as follows: in a 500-mm three-necked flask under nitrogen flow [2,
11.8 f (48.8 mmol) of 5-dibromothiophene, 11.4 f (1
16 mmol), add 200 mmol of diethylamine, and
Stir to mix. To this was added 1.1 f (1.6 mmol) of dichlorobis(triphenylphosphine)palladium and 0.3 f (1.6 mmol) of cupric io9ide,
The mixture was heated and stirred at 60°C for 4 hours. After cooling, the insoluble diethylammonium bromide tF was separated, and the liquid f was dried to dryness under reduced pressure, and the residue was extracted with 50% of benzene. After drying the benzene solution under reduced pressure, 51
The mixture was stirred under reflux for 1 hour with activated carbon. When activated carbon is separated from P and acetone is distilled off, 2.5% of white needle-like crystals are left as a residue.
-bis(trimethylsilylethynyl)thiophene11.
5f (41.5 mmol) was obtained.

Then, 11.5 f (41.5 mmol) of the obtained 2,5-bis(trimethylsilylethynyl)thiophene and 70 methanol were charged into a 500 m three-neck flask under a nitrogen stream. A saturated methanol solution of 70-potassium fluoride was added dropwise to this, and the mixture was heated and stirred at 40°C for 3 hours.
After methanol was then distilled off under reduced pressure, the residual liquid was extracted with diethyl ether to remove residual potassium fluoride, and diethyl ether was further removed under reduced pressure to form a pale yellow liquid.
5-jethynylthiophene 2.9 F (19.4 mmol) was obtained.

(2.25 f.
(17.1 mmol), 2゜6-dipromoviridine4.
04 f (17,1 glimole), diethyl amine 5O
-1N-menylphosphine) palladium 0.24F (0
, 34 mmol) and cupric iodide 0.033F (0,
17ml) was added, and the mixture was heated and stirred at 60°C for 2 hours.
After the reaction is completed, the solution is concentrated under reduced pressure, and the generated solid t?
Wash with 300 mg of t-hydrochloric acid (371!) of t-TR-containing water, and then wash with 300 mg of 9m sodium hydroxide methanol solution to obtain a dark brown powder. I got Of.

The IR spectrum (Nujol method) of this dark brown powder shows CH derived from C, CM groups near 3300m-' observed in the raw material 2,5-jethynylthiophene.
Stretching vibration (ν(CM)) has disappeared, and at 2100 cm
The absorption based on the CIC coupling near -' was observed shifted to a higher wave number at 1004-'.
Since a new absorption characteristic of pyridine rings appears near t-', the production tube is a polymer with the following structure, which has alternating -C=C- groups and thiophene rings or pyridine rings. It has been determined.

Note that the IR of the linear conjugated alternating copolymer obtained in this example
The characteristic absorption of the spectrum is 3050 e, 2200 e
x, 1570CIl, 1550m, 800
I-”, 720α-1 and 660fi-”.

Further, the number average molecular weight (Mn') was 20.000, the degree of polymerization was 9F, and the melting point (decomposition point) was 300°C or higher.

Example 2 Example 1 (2,5-dibromothiophene 4.14F (17,1
3.25F in the same manner as in Example 1 using
A dark brown powder was obtained.

Measurement of the IR spectrum revealed that 3300. Nearby CICHftK
The absorption based on CTC coupling has disappeared, but the absorption based on CTC coupling has been shifted to the higher wavenumber side by 60°-1 to 2160m.
K was observed, and the absorption specific to the thiophene ring was 798tx''''
1, the product was determined to have the following structure.

Note that the IR of the linear conjugated alternating copolymer obtained in this example
The characteristic absorption of the spectrum is 2160m-', 79801
1-'% 720 (m-' and 660 CIL-').

Also, the number average molecular weight country 1') is 11,000, and the weight e
ft was 52, and the melting point (decomposition point) k was 300°C or higher.

Example 3 (1) 2,6-dinitinylpyridine is Synthesi
m, p. 627 (1980) as follows: 24.8 f (104.7 mmol) of 2,6-dibromopyridine, trimethylsilyl Add 22.6 f (230.3 mmol) of acetylene and 250 dt of diethylamine and mix well with stirring.To this, 1.6 f (2.3 mmol) of dichlorobis(triphenylphosphine)palladium and 0.44 f of steel iodide. (2.3 mmol) was added and stirred at room temperature for 3 hours. After the reaction was completed, insoluble diethylammonium bamide t-P was separated and dried under r*t-reduced pressure.
The residue is extracted with 100 ml of benzene.

When the benzene solution was dried under reduced pressure, a brown solid was obtained.
5f was obtained. Mixture 19.5F containing 2,6-bis(trimethylsilylethynyl)pyridine thus obtained
and 100 d of methanol were charged into a 300-meter three-necked flask under a nitrogen stream, and 1 liter of IN potassium hydroxide aqueous solution was added to the flask.
45- was added dropwise, and the mixture was stirred at room temperature for 1 hour. After methanol was then distilled off under reduced pressure, the residue was extracted with diethyl ether, and the diethyl ether was distilled off under reduced pressure to obtain a brown solid. When this was sublimed at 40° C. under I Tore, 2,6-dinitinylpyridine 6.6f (52 mmol) was obtained as colorless needle crystals.

(2) 2.50f of the above 2,6-dinitinylvinodine
Example 1
A black brown powder of 3.602 g was obtained by pressing in the same manner as above.

According to the measurement of the IR spectrum, the absorption based on the C=CH group near 3300 cm'' observed in 2,6-dinitinylpyridine disappeared (%), but the absorption based on the c=c bond (8) disappeared. Shift the absorption by 180 cs to the higher wavenumber side to 2180 cs.
t-''K was observed, and from the presence of a pyridine ring-specific σ) absorption near 1550 cm-', the product was determined to have the following structure.

Note that the IR of the linear conjugated alternating copolymer obtained in this example
Characteristic absorption of spectrum tt3050cR-', 2180
m-", 1565 shin-', 1545m-", 120
0m-', 805crIL''''1 and 720m-'
'is.

Further, the number average molecular weight (I') was 12,000, polymerization [n was 59, and the melting point (decomposition point) was 300°C or higher.

Example 4 Magnesium (If, 41 mmol), ethyl bromide (4,4F, 41 mmol) 50 m of a tetrahydrofuran solution of the ethylmagnesium bromide thus prepared
Ks 2-5-jethinylthiophene (2,64f,
A THF solution of 20 mmol (17 mol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. Into the digrignard reagent solution of 2,5-diethynyltheophene thus obtained, 2.6
- dibromopyridine (4-7ts20 mol) and
Catalysts palladium acetate (0.045F, 0.2 mmol) and triphenylphosphine (0.11F, 0.4 mmol) were added and the reaction was refluxed for 3 hours. 37 悌) f: Washed with 300 ml of water and further washed with 300 ml of sodium hydroxide methanol solution to obtain 3.2 f of dark brown powder.

As a result of measuring the IR spectrum of this dark brown powder, as in Example 1, it was determined that it was a polymer having the following structure.

The number average molecular weight (response) is 14,000, and the degree of polymerization is n.
was 68, and the melting point (decomposition point) was 300°C or higher.

Claims (1)

[Claims] (1) Repeating structural unit represented by the following general formula l -Ar-CmC-Ar'-CswC-I (wherein r and Ar' are the same or different heteroaromatic rings) Completely blind linear conjugated alternating copolymer. (A jetynyl heteroaromatic ring compound represented by the 4th general formula HC=C-Ar-C=CHII (in the formula, mr is a heteroaromatic ring) is prepared in the presence of an amine under a palladium compound and a copper compound catalyst. Then, the following formula ■
is a heteroaromatic ring that is the same as or different from the above Ar, and X is a halogen. A method for producing a linear conjugated alternating copolymer having a repeating structural unit represented by CwiC-I (where Ar and Ar' are as described above). (3) The following general formula ■ X'MgC! ! IC-Ar-C=CMgX'
Pi (wherein Ar is a heteroaromatic ring% and a heteroaromatic ring that is the same as or different from Ar;
X is the same or different halogen as X' and Ar' are as described above) A method for producing a linear conjugated alternating copolymer having a repeating structural unit.