JPS60112820A - Preparation of polyarylene vinylene - Google Patents

Abstract

PURPOSE:To prepare a polyarylene vinylene in high yield easily without causing problems with respect to reaction, by reacting a haloarylene compound with a specific disilane as a homocoupling agent in the presence of an organometallic complex catalyst. CONSTITUTION:A haloarylene compound shown by the formula I (X is chlorine or bromine; R and R' are H, halogen, alkyl, or aryl; Ar is arylene) is reacted with a disilane shown by the formula R''mSi2Cl6-m (R'' is alkyl; m is 0-6) as a homocoupling agent in the presence of an organometallic complex catalyst, to prepare a polyarylene vinylene shown by the formula II (R, R', and Ar are as shown for the formula I ; n is positive integer). Bivalent or zero valent palladium complex compound is used as the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyarylene vinylene, and more particularly to a novel method for producing polyarylene vinylene using disilanes as a homocoupling agent.

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. Attempts are being made. For example, (1) Wlttlg reaction, that is, the use of the condensation reaction of bisphosphorane and dialdehyde [(■')s P''-OH, -hr-am*-p+c@
) 3) 2X-+0HO-Ar'-0) (0(2) Knoevenagel reaction, i.e., the use of the direct bonding reaction between an active methyl group and an aldehyde H30-A r -OH3+OHO-A r' -OH
O→(-A r -OH= OH-A r' -OH=
OH) (3) Utilization of dehydrohalogenation reaction in which various strong bases (1; -BuOK, NaNH2, NaH, etc.) act on bishalomethylarylene compounds X -OH2-A r OH2-X→+Ar-0H= C
! Methods such as H) are known.

Although such a method is an excellent synthetic method and has high practical value, for example, the use of the Witzig reaction in (1) is useful when a substituent that has a substituent that reacts with the ylide, such as an amine group, a carbonyl group, or a hydroxyl group, is used. Since the compound cannot be synthesized and the product is a mixture of cis and trans isomers, isomerization from cis to trans isomerization is required to improve oxidation stability, softening point, electrical conductivity, etc. is necessary.

In the Knebenagel reaction (2), the methyl group is a nitro group,
Since the reaction will not proceed unless activated by an electron-withdrawing group such as an amine group, the selection of raw materials to be used is limited.

In the dehydrohalogenation reaction (3), the selection of raw materials is limited because the polymer contains an active .

Each of them has drawbacks. Therefore, the present inventors solved the reaction problems of polyarylene vinylene,
Various studies were conducted with the aim of finding a suitable manufacturing method.

As a result, they discovered a new method for producing polyarylene vinylene that can be easily produced with good yield, and completed the present invention.

In the method for producing polyarylene vinylene of the present invention, or bromine, R and R' represent hydrogen, nitrogen, an alkyl or aryl group, and Ar represents an arylene group. ) as an organometallic complex catalyst and a homocoupling agent, the general formula R'mSI2016-
RRI RRI R, R' and Ar are the same as above, n is Represents a positive integer. ) is a method for producing polyarylene vinylene.

In the production method of the present invention, an organometallic complex catalyst and a homocoupling agent are required, and C, divalent or zero-valent palladium complexed foods are preferably used as the organometallic complex catalyst.

Some specific examples of haloarylene compounds of general formula [1] that can be used in the present invention include hexadi 1:I rho p
-xylene, hexachloro-m-xylene, α, α,
α', α'-tetrachloro-p-xylene, α, α, α
', α'-tetrabromo-m-xylene, α, α.

a', α'-tetrabromo 〇-xylene, perchloro-p-xylene, 2,5-dimethoxy-α, α, α'.

a'-tetrachloro-p-xylene, 2. '5'-bis(dichloromethyl)-p-terphenyl, 1,5-bis(α,α-dichlorobenzyl)naphthalene, 4.4’-
Bis-dichloromethyl-biphenyl, 4゜4'-bis(
α, α-Cyfromobenzyl) diphenyl ether, 1.
4-bis(α,α-dichlorobenzyl') -2,5-
Dimethoxybenzene, 9.10-bis(α,α′-dichlorobenzyl)anthracene, 9.10-bis(α,α
'-dibromoethyl)anthracene, 2,7-bis(α
, α-dichlorobenzyl)fluorene, 3,6-bis(
dichloromethyl)-9-methylcarbazole, bis(α
, α-dichlorobenzyl)thianthrene, 4.4'-bis(cyclo-4-bromophenyl)biphenyl, 4.
4'-bis(dibromomethyl)stilbene, and analogs and mixtures thereof are honored.

In the production method of the present invention, a divalent or zero-valent palladium complex compound is preferably used as the organometallic complex melting medium coexisting in the reaction system with the haloarylene compound represented by the general formula [1]. For example, dichlorobis(hendinitrile)palladium (F), dibromobis(triphenylphosphine)palladium (I
t), bis(acetylacetonato)palladium (■)
, dichlorobis(tri-n-butylphosphine)palladium (It), ) lance-dimethylbis(triphenylphosphine)palladium (■), C μm chloro-dichlorobis(triphenylphosphine)palladium (Il)
), tetrakis(triphenylphosphine)palladium(0'), carbonyltris() IJphenylphosphine)palladium(0), bis(dibenzylideneacetone)palladium(0), chloro(4-nitrophenyl)
Bis(tri-tolylphosphine)palladium(11
), iodo(phenyl)bis(triphenylphosphine)palladium(II), and a complex consisting of a combination of palladium acetate and triarylphosphine. Particularly preferred is tetrakis(triphenylphosphine)palladium(0). Palladium metal can also be used in place of such organometallic complexes, if desired.

Examples of the disilanes of the general formula [Kawa] that can be used as homo-coupling agents that coexist with the no-roarylene compound of the general formula [I] in the reaction system include hexamethyldisilane, chloropentamethyldisilane, 1. 2-dichloro-1,1,2,2-tetramethyldisilane, 1,
1-dichloro-1゜2,2,2-tetramethyldisilane, 1.1.1-)lichloro-2.2.2-)limethyldisilane, 1.1.2゜2-tetrachloro-1,2-
Dimethyldisilane, 1,1.1.2-tetrachloro-2
, 2-dimethyldisilane, pentachloromethyldisilane, hexachlorodisilane, etc., and these disilanes can be mixed and used as a mixture.

In the production method of the present invention, the amount of the organometallic complex and the disilane represented by the general formula (n) to be used with respect to the no-roarylene compound represented by the general formula [l] is 20 mol from the organometallic complex Q, 005. %, preferably 0.05 to 10 mol %, 1 to 20 times the mole of disilanes, preferably 2 to 10 times the mole. Therefore, the reaction temperature as reaction conditions in the production method is 50°C to 200°C, preferably 60°C to 150°C, and the reaction time is 0.5 hours to 60 hours, preferably 2 hours to 20 hours. . This reaction is advantageously carried out under an inert atmosphere in a reaction solvent, preferably an inert solvent. Such reaction solvents include, for example, N,N-dimethylformamide, dimethylacetamide, toluene, xylene, mesitylene, chlorobenzene, o-dichlorobenzene, N-methyl-2-
Pyrrolidone, 1,5-dimethyl-2-imidazolidinone, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, dioxane, etc. can be used.

The polyarylene vinylene of the general formula (1) obtained by the production method of the present invention is generally a thermoplastic polymer with excellent high temperature stability, and varies considerably depending on the selection of the haloarylene compound of the general formula (1). However, some of them can be molded by a casting method in an organic solvent and can also be made into a film. In addition, similar to polymers produced by other methods, it can be used for any purpose by taking advantage of its useful properties such as heat resistance, electrical conductivity, and optical properties.

The production method of the present invention has a wider range of usable compounds than conventional methods, and by utilizing the production method of the present invention, it is also possible to produce polymers that were previously impossible to produce. .

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

Example 1 A mixture consisting of 1.25 nlD parts by weight of hexachloro-p-xylene (the same applies hereinafter), 2.64 parts of hexamethyldisilane, 018 parts of tetrakistriphenylphosphine palladium, and 5 parts of mesitylene was heated to a temperature of 160°C while stirring under a nitrogen atmosphere. The reaction was carried out at a temperature of 150°C to 150°C for 7 hours. After the reaction, the reaction mixture was cooled and the resulting precipitate was sufficiently washed with toluene and then acetone to obtain 69 parts of yellow polymer o. The obtained polymer was confirmed to have a structure with an infrared absorption spectrum of 1, and was insoluble in aromatic solvents. The infrared absorption spectrum is shown in FIG.

Example 2 α, α, α′, α′-tetrabromo-〇-xylene 12
．． A mixture consisting of 11 parts of hexamethyldisilane, 2.9 parts of tetrakistriphenylphosphine palladium, 0.12 parts of tetrakistriphenylphosphine palladium, and 7 parts of mesitylene was heated to 100°C for 8 hours with stirring under a nitrogen atmosphere, and then heated to 140°C. The mixture was heated to 150° C. for 4 hours, and then the temperature was raised to 150° C. for 3 hours. After the reaction, the reaction mixture is cooled, poured into methanol, the precipitates are separated, thoroughly washed with methanol, and dried at 80°C under reduced pressure to obtain a yellow polymer. 046 copies were obtained. The obtained polymer was analyzed by infrared absorption spectrum.

Example 3 1.07 parts of a yellow polymer was obtained according to the method of Example 2, except that 1.98 parts of 1,4-his(α,α-dichlorobenzyl)benzene was used.

[Brief explanation of the drawing]

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

Claims (1)

[Claims] A haloarylene compound represented by RR' (wherein, X represents chlorine or bromine, R and R' represent hydrogen, halogen, alkyl or aryl group, and Ar represents an arylene group) is used as an organometallic complex catalyst. and as a homo-coupling agent the general formula R″mS 12
016-y, [II:II (wherein, R' is an alkyl group and m is an integer from 0 to O). R, R' and Ar are the same as above, and n represents a positive integer.) A method for producing polyarylene vinylene. 2. The production method according to claim 1, wherein the organometallic complex catalyst is a divalent or zero-valent palladium complex compound.