Polyanils

Details Polyanils Polyanils

1994-12-02

1996-06-25

Mullis, Jeffrey

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From phenol, phenol ether, or inorganic phenolate

528229, 528332, 528318, 528312, 528422, C08G 7300

Patent

active

055300871

DESCRIPTION:

BRIEF SUMMARY
DESCRIPTION

The present invention relates to polyanils of the general formula ##STR5## where
R.sup.1 is C.sub.1 --C.sub.24 -alkyl, C.sub.1 -C.sub.24 -alkoxy, Cl, Br, CF.sub.3 or NO.sub.2,
R.sup.2 is para-phenylene, a fused aromatic ring system of 10 to 30 carbon atoms or ##STR6## R.sup.3 is a chemical bond S, O, NH, CH.sub.2, CH.dbd.CH, CO, SO or SS, and ##STR7## where X.sup.- is ClO.sub.4.sup.-, BF.sub.4.sup.-, AsF.sub.6.sup.- or ##STR8## and R.sup.4 is C.sub.1 -C.sub.8 -alkyl.
The present invention furthermore relates to processes for the preparation of these polyanils and to their use as electrically conductive materials and for nonlinear optical purposes.
The Handbook of Polym. Synthesis, Part B, 1390 (1992), edited by H. R. Kricheldorf, Marcel Dekker, New York, discloses that aniline can be converted by oxidation into aniline black, also referred to as polyaniline. However, these polymers are not homogeneous and, in addition to the units of the type ##STR9## also contain quinoid structures, and these products are furthermore contaminated by other oxidation products and, owing to their poor solubility or insolubility, are virtually impossible to purify and characterize exactly.
It is an object of the present invention to provide polymer systems which do not have these disadvantages and have extensive .pi. conjugation.
We have found that this object is achieved, according to the invention, by the polyanils defined at the outset. We have also found processes for the preparation of these polyanils and their use as electrically conductive and nonlinear optical materials.
Preferred polyanils of the general formula I are the compounds in which R.sup.1 is a solubilizing group, in particular C.sub.1 -C.sub.13 -alkyl or C.sub.1 -C.sub.13 -alkoxy. R.sup.2 is preferably para-phenylene, naphthylene, anthracylene or ##STR10## and R.sup.3 is S, NH or CH.dbd.CH. Para-phenylene is particularly preferred. n is preferably from 10 to 50.
In the case of the acid addition salts of the general formula II, preferred compounds are those in which R.sub.1, R.sub.2, R.sub.3 and n have the meanings stated as being preferred in the case of the polyanils of the general formula I. The anion X.sup.- is in particular ClO.sub.4.sup.- or ##STR11## and R.sup.4 is preferably C.sub.1 -C.sub.4 -alkyl.
The novel polyanils can be prepared by a method in which, in a first step, a compound of the general formula III ##STR12## is subjected to a Vilsmeier-Haack-Arnold reaction to give an amidine which is converted in a second step, by the addition of an aromatic diamine, into a polyanil of the general formula I.
Compounds of the general formula III and processes for their preparation are known per se to a person skilled in the art. Where R.sup.1 is alkoxy, it is possible, for example, to start from the corresponding hydroxy compound ##STR13## and to convert it into the alkoxy compound by reaction with an alkyl halide.
In the Vilsmeier-Haack-Arnold reaction, dimethylformamide and POCl.sub.3 are added to compounds of the general formula III, an amidine or, when, for example, NaClO.sub.4 is added, an amidinium salt being formed. The molar ratio of dimethylformamide to the compounds of the general formula III is as a rule from 20:1 to 2:1, preferably from 6:1 to 4:1, and the molar ratio of POCl.sub.3 to the compounds of the general formula III is from 5:1 to 1:1, preferably from 4:1 to 2:1. Further information on the Vilsmeier-Haack-Arnold reaction is to be found in Houben Weyl VII/1, [1954], 29-36, Georg Thieme Verlag, Stuttgart.
In a second step, the resulting amidine or amidinium salt can then be converted into the polyanils of the general formula I or into their acid addition salts of the general formula II. For this purpose, the amidine or the amidinium salt is reacted with an aromatic diamine of the general formula
The preferred radicals R.sup.2, which were stated in the case of the polyanils, are the consequence of the diamines preferably used here.
The reaction of the amidine or amidinium salt with the aromatic diamine can be carried out in

REFERENCES:
Handbook of Polyer Synthesis, Part B, Ed. Kricheldorf (1992), Naarmann et al., 1353-1435.
Patent Abstracts of Japan vol. 10, 28 (C-326) (2085) Feb. 4, 1986--JP 60 181 127.

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