JPS5832629A - Preparation of polyarylene-ethynylene - Google Patents

Abstract

PURPOSE:To obtain the titled compound having heat resistance, electrical conductivity, photoconductivity, etc., easily, in high yield, by reacting a specific haloethynyl arylene compound in the presence of a catalyst and a hydrogen halide acceptor. CONSTITUTION:The objective compound of formulas V{Ar is formula II-IV, etc.; Y is H, R, N(R)2, etc.[R is H, (cyclo)alkyl, etc.]; Z1 is -N= or -CH=; Z2 is -O-, -S-, SO2, etc.; m is 0-6; n is positive integer}is prepared by reacting a haloethynyl arylene compound of formulaI(X is Br or I) (e.g. p-bromophenylacetylene) in a solvent such as xylene in the presence of a catalyst (e.g. a combination of palladium acetate the tri-o-tolylphosphine) and a hydrogen halide acceptor (e.g. piperidine) at 75-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyarylene ethynylene.

Since polyarylene/ethynylene is a conjugated aromatic polymer containing a carbon-carbon triple bond, it is expected to have useful properties such as heat resistance, 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 IH & method of polyarylene/ethynylene of the present invention is as follows:
By reacting a haloethynylarylene compound represented by the general formula X-Ar-C=CH in the presence of a catalyst and a hydrogen halide scavenger, the general formula (Ar-CIC)
Polyarylene... ethynylene shown in a good yield,
It is easy to manufacture.

(4) (II) I) (Foundation) Leap (6)
, compensation) cVID, and each Y is hydrogen, -R91l -N-C-*', -Lo-R1,, -5RI, -N
o, , -8o, H.

and -8o1M (each R is hydrogen or alkyl).

Cycloalkyl, aryl, aralkyl 1-1
selected from the group consisting of alkyl-nor radicals containing 6 carbon atoms, where R' is alkyl, cycloalkyl, aryl, aralkyl.

and an alkaryl group containing 1 to 16 carbon atoms, and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium. is; each 2
Is 1 selected from the group -Ngo and -C'H-? -CH,= selected from the group consisting of -N-;
CH-, -CmiC2, -N2N, ,7. C
j(,”-=NT.

Ma is selected from the group consisting of 宕-C-; When 21 in formula (1) is 10H=, m is an integer between θ and 6, and z
When l is -N2, it is an integer of 0 to 5; formula (II)
When 2. of is -CH"=, m is an integer from 0 to 6; when zl is -N-, it is an integer from 0 to 5; formula QI
[), (Ml, (V), (VD '7) m is θ~
is an integer of 6; m in formula (4) is an integer of 0 to 2;
m in formula (4) is an integer of 0 to 4; P is an integer of 0 to 1; X is bromine or iodine; n is a positive integer. ] 1. 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 8th-class amines, and basic salts such as sodium bicarbonate and sodium carbonate.

Some specific examples of haloethynylarylene compounds represented by the general formula Fenino"t4 7'Romo4'-ethynylbiphenyl ether, 2-bromo4-ethynylthiophene, 2-bromo-6-'ethynylthiophene, 8-bromo-N-ethyl-6-nitynylcarpazole, 2- Promo 7-nitinylfluorene, 8-bromo-6-nitinylcyhenzothiophene, 2-bromo 6-nitinylhyricine, 4-ethynyl-4'-iodoambenzene, 4-bromo 4'
-ethynylazoxybenzene, 1-ethynyl-4-iodo-naphthalene, 2-ethynyl-5-iodopyrazine,
6-cyclohexyl-4-ethynyl-1-iodo/thracene, 8-promo N-ethyl-7-nitinylphene
Some include nothiazi:y,4-promo 4''-ethynyl-P-terphenyl and the like and mixtures thereof.

In addition, ``In the manufacturing method of the present invention, the general formula (however, A
When reacted in the presence of a halobinyl arylene compound, where r' is the same as the above Ar, and R and RL are each hydrogen, methyl group, or ethyl group (1-0), a carbon-carbon double bond, is a conjugated aromatic polymer containing triple bonds,
The general formula % can be produced.

The method of the present invention uses a haloethynylarylene compound represented by the general formula X-Ar-CNCH, such as palladium acetate or triarylphosphine.

The reaction is carried out in the presence of an 8th class amine at a temperature of 75 DEG C. to 150 DEG C., often during winter, and is completed in 1 hour to 60 hours.

Triarylphosphines include triphenylphosphine/trilotrylphosphine.

Tris(2,5-diisopropylphenyl)phosphine, tri-alpha-naphthylphosphine, tris(2,a4,
5-tetramethylphenyl)phosphine, tris(2-
Methyl-5-t-butyl)phosphine, tris(P-
Examples include carbomethoxyphenyl)phosphine, in particular trilotrylphosphine, tris(2-methyl-5-t-butylphenyl)phosphine/
It is preferable to use The triarylphosphine used in the present invention is suitably α5 to 10 moles per mole of palladium acetate. Further, the appropriate amount of palladium acetate to be used is α5 to 4 mole of the amount of haloethynylarylene used.

Secondary amines and 8th-class amines are used as scavengers for generated hydrogen halides, but diethylamine, di-n-
Butylamine, piperidine.

Commonly used amines such as morpholine, triethylamine, tri-n-butylamine, triamylamine, and tetramethylethylenediamine may be used, and the amount used is usually a little in excess of the equivalent molar amount of hydrogen halogenide generated.

Common reaction solvents are used, such as N,N-dimethylformamide, dimethylacetamide, toluene, xylene, and chlorobenzene.

0-dichlorobenzene, N-methyl-2-pyrrolidone,
L8-dimethyl-2-imidazolidinone, dimethyl sulfoxide, acetonitrile, etc. are used.

Both end groups of the polymers obtained according to the invention are usually hydrogen, bromine or iodine, in particular the end group on the ethynyl side is usually hydrogen. In addition, the average degree of polymerization of the polymer is 2 or more,
In particular, 10 or more is preferable. Polymers are generally thermoplastics of excellent high temperature stability and vary considerably depending on the reactants selected, with some being soluble in solvents and even capable of being made into silica films by casting methods. .

The method of the present invention can be used in a wide range of compounds, and due to the efficiency of 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 photoconductivity, and can be used for any purpose.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Example 1 (Synthesis of P-bromo-L2-dibromoethylbenzene)
P-bromostyrene (Aldrich ff) l.

(parts by weight, same hereinafter) was dissolved in 20 parts of chloroform, and then a solution of 4 parts of bromine a dissolved in 10 parts of chloroform was added dropwise at 0 to 4°C. After reacting for 30 minutes at the same temperature, chloroform and unreacted bromine were distilled off (P-bromo-L2-dibromoethylpenzene 1
'I got 19 copies.

(Synthesis of p-bromo-phenylacetylene) A solution in which 1.1 part of metallic potassium was added to 250 parts of t-butanol was heated until reflux, and P-bromo L 2-,
9 parts of 1'L of dibromoethylbenzene was added. After reacting for 1 hour, the reaction mixture was poured into 1000 d of ice water, and then dichloromethane was added to extract the product. Dichloromethane was distilled off and the residue was evaporated under reduced pressure (2 wHf) from 60 to
By sublimation at 80°C, 789 parts of P-bromo-phenylacetylene was obtained. (Melting point 6a4°C) [Synthesis of polymer] 102 parts of P-bromo-phenylacetylene L 09 W r piperi 2F, 0.018 parts of palladium acetate.

A mixture consisting of 21 parts of tri-0-tolylphosphine 00 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 156 parts of a yellow polymer.

In the engineering R chart of a polymer, ν(C
al) is recognized as only a small absorption, ν(Cm
The absorption based on C) shows a composition at 2200 cm'.

The process R chart is shown in Figure 1. ' Example 2 (N-ethyl-3-bromo-6-formylcarno (Sorno synthesis)) N-ethyl-8-formylcarnoxole (
(manufactured by Aldrich) was dissolved in 170 parts of acetic acid, and 165 parts of bromine was added dropwise while stirring. 10
After reacting for a minute, the reactant was poured into ice water, and the precipitate was thoroughly washed with water and then recrystallized from ethanol to obtain 260 parts of N-ethyl-8-bromo-6-formylcarno; 86%).

(8-7' lomo N-ethyl-6-pinylcarno(n°-luno synthesis) 4.5 parts of dry dimethyl sulfoxide was added to 026 parts of sodium hydride (50%) under a nitrogen atmosphere, and while stirring, hydrogenated at 75°C. The mixture was heated until gas evolution ceased. After cooling in an ice and water bath, 889 parts of methyltriphenylphosphonyl iodide powder was added. The resulting red solution was stirred at room temperature for 10 minutes, then dimethyl N-ethyl- dissolved in sulfoxyr°
4 parts of 8-bromo 6-formylcarpadules ao were added dropwise. After stirring at 60° C. for 90 minutes, 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-N.
-ethyl-6-vinyl-carbazole 526 parts (yield 8
8ch) was obtained. (Melting point 95°C) [Synthesis of 8-bromo-N-ethyl-6-nitinyl-carhasol] After dissolving 388 parts of 8-bromo-N-ethyl-6-vinyl-carbazole in 20 parts of chloroform, stir at 0°C. So bromine 5
94 parts were added dropwise. By distilling off chloroform and unreacted bromine, 3-bromo-6-dipromoethyl-N-ethylcarbasol a'xs was added. A solution in which 148 parts of metallic potassium was added to 180 parts of n-butanol was refluxed. 8-Furomo6-dipromoethyl-N-ethylcarbazole &1
8 parts were added dropwise little by little. After dropping and reacting for 1 hour, the reaction mixture was poured into ice water. The precipitated solid was collected and dried to obtain 175f of 8-promo-N-ethyl-6-nitinyl-carbazole.

[Synthesis of polymer]

100 parts of 8-7' lomo N-ethyl-6-ethynyl-carbazole, 0,008 parts of palladium acetate, 0,021 parts of tri-tolylphosphine.

A mixture consisting of 196 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 070 parts of a polymer having the following structural formula.

The R chart is shown in Figure 2.

Example 8 (Synthesis of 8-bromo-N L-nL dodecyl-6-vinyl-carbazole) Using N-n-dodecyl-8-formylcarbazole in place of N-ethyl-8-formylcarbazole in Example 2 The method of Example 2 was followed except that 8-bromo-
N-n-)"7" sil-6-pinylucarbazole was obtained.

[Synthesis of polymer]

1188 parts of 8-bromo-N-n-dodecyl-6-vinyl-carbazole, 086 parts of P-bromo-phenylacetylene obtained in Example 1, tri-tolylphosphine α
Part 024, acetate badge.

A mixture consisting of 6009 parts of sea urchin, 151 parts of piperidine, and 4 parts of xylene was polymerized according to the method of Example 1 to obtain 022 parts of a polymer.

In the engineering R spectrum of the polymer, absorption based on ν(C!IC) is observed at 2200ffi', and absorption based on CH out-of-plane bending absorption attached to the trans double bond is observed at 96QcIn'. This indicates the formation of a polymer having the following structural formula.
As shown in the figure.

[Brief explanation of the drawing]

FIGS. 1 to 3 are R charts of the Mizumoto polymers produced in Examples 1 to 8, respectively.

Claims (1)

[Claims] L General formula +A characterized in that a haloethynyl arylene compound represented by the general formula X-Ar -Cm CH is reacted in the presence of a catalyst and a hydrogen halide scavenger.
A method for producing polyarylene ethynylene represented by rC-C,h. (I) (If) [) (view) (4) (4), each Y is hydrogen, -R9 and -8o, M (each R is hydrogen, alkyl, cycloalkyl, aryl 2.
selected from the group consisting of aralkyl and alkaryl groups containing 1 to 16 carbon atoms, where R' is alkyl, cycloalkyl, aryl. selected from the group consisting of aralkyl and alkaryl groups containing 1 to 16 carbon atoms; M is sodium, potassium; 3 selected alkali metals from the group consisting of lithium; each 21 is -
selected from the group consisting of N= and -CH=; z8 is selected from 10-9; G is selected from 10+,
-N-. 0 -CM-CH-', -Cth C-, -N=N-, -CH,
=N-9-C-, and when 21 in equation (1) is -CU=, m is an integer between θ and 6, and when zl is -N= is an integer from 0 to 6; the formula (when 21 of IO is =CH-, m is an integer from θ to 6, and when zl is -N=, it is an integer from θ to 6, and one set m in E), W), (V), and (B) is an integer from 0 to 6; m in formula (Vl) is an integer from θ to 2;
In (2), m is an integer of 0 to 4; P is an integer of θ to 1; X is bromine or iodine; and pan is a positive integer. 2. The method of claim 1, wherein the catalyst comprises a combination of palladium acetate and triarylphosphine. 1. The method according to claim 1, wherein the hydrogen halide scavenger is a secondary amine or an 8th-class amine.