Azo dye polymers

Abstract

Azo dye polymers useful in nonlinear optics contain as characteristic monomer units radicals of the formulae I, II, III and IV ##STR1## where D is the radical of a heterocyclic diazo component, R 1 and R 2 are each hydrogen, C 1 -C 6 -alkyl or substituted or unsubstituted C 1 -C 6 -alkoxy, and R 2 may also be C 1 -C 4 -alkanoylamino, R 3 is hydrogen, C 1 -C 6 -alkyl, C 5 -C 7 -cycloalkyl or C 3 -C 4 -alkenyl, R 4 is hydrogen, deuterium, methyl, trideuterated methyl or chlorine, R 5 is hydrogen or deuterium, Y 1 and Y 2 are each substituted or unsubstituted C 2 -C 10 -alkylene, W is oxygen, imino or C 1 -C 4 -alkylimino, and X is hydroxyl, substituted or unsubstituted C 1 -C 6 -alkoxy, phenoxy, amino or mono- or di(C 1 -C 4 -alkyl)amino, and have an average molecular weight of from 1,000 to 100,000.

We claim: .[.1. An azo dye polymer containing as characteristic monomer unit radicals of the formulae I, II, III and IV ##STR32## where D is the radical of the diazo component derived from a five-membered aromatic heterocyclic amine having one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur in the heterocyclic ring and optionally fused to a benzene, thiophene, pyridine or pyrimidine ring, 
     
        molecular weight of the polymer being from 1,000 to 100,000..]..[.2.  An azo dye polymer as claimed in claim 1, wherein D is derived from a heterocyclic amine of the pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadiazole, benzofuran, benzothiophene, benzimidazole, benzoxazole, benzothiazole, benzoisothiazole, pyridothiophene, pyrimidithiophene, 
     
     
        thienothiophene or thienothiazole series..].3. An azo dye polymer as claimed in claim 1, wherein in formula (I) D is ##STR33## R 1  is hydrogen, R 2  is methyl, R 3  is ethyl, Y 1  is 
     
     
        hexylene, W is oxygen and R 4  is methyl. .Iadd.4.  An azo dye polymer containing as characteristic monomer units radicals of the formulae I, II, III and IV ##STR34## wherein D is the radical of a diazo component derived from a compound selected from the group consisting of: ##STR35## wherein .sup. 1 is nitro, cyano, C 1  -C 6  -alkanoyl, benzoyl, C 1  -C 6  -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl or a radical of the formula --CH═T, where T is the radical of an acidic CH compound, .sup. 2 is hydrogen, C 1  -C 6  -alkyl, halogen, hydroxyl, mercapto, unsubstituted or phenyl- or C 1  -C 4  -alkoxy-substituted C 1  -C 6  -alkoxy, substituted or unsubstituted phenoxy, unsubstituted or phenyl-substituted C 1  -C 6  -alkylthio, substituted or unsubstituted phenylthio, C 1  -C 6  -alkylsulfonyl or substituted or unsubstituted phenylsulfonyl,   1 3  is cyano, C 1  -C 4  -alkoxycarbonyl or nitro,   1 4  is hydrogen, C 1  -C 6  -alkyl or phenyl,   1 5  is C 1  -C 6  -alkyl or phenyl,   1 6  is cyano, C 1  -C 4  -alkoxycarbonyl, C 1  -C 6  -alkanoyl or halogen,   1 10  is phenyl or pyridyl,   1 11  is trifluoromethyl, nitro C 1  -C 6  -alkyl, phenyl, unsubstituted or phenyl-substituted C 1  -C 6  -alkylthio or C 1  -C 4  -dialkylamino,   1 12  is C 1  -C 6  -alkyl, phenyl, 2-cyanoethylthio or 2-(C 1  -C 4  -alkoxycarbonyl)ethylthio, and   1 13  is hydrogen, nitro or halogen;   R 1  and R 2  are each independently of the other hydrogen, C 1  -C 6  -alkyl or C 1  -C 6  -alkoxy optionally substituted by phenyl or C 1  -C 4  -alkoxy, and R 2  may also be C 1  -C 4  -alkanoylamino,   R 3  is hydrogen, C 1  -C 6  -alkyl, C 5  -C 7  -cycloalkyl or C 3  -C 4  -alkenyl,   R 4  is hydrogen, deuterium, methyl, trideuterated methyl or chlorine,   R 5  is hydrogen or deuterium,   Y 1  and Y 2  are each independently of the other C 2  -C 10  -alkylene optionally interrupted by 1 to 3 oxygen atoms in the ether function of imino or C 1  -C 4  -alkylimino groups,   W is oxygen, imino or C 1  -C 4  -alkylimino, and   X is hydroxyl, C 1  -C 6  -alkoxy, trideuterated methoxy, 2,3-epoxypropoxy, phenoxy, amino or C 1  -C 4  -mono- or -dialkylamino, the proportion of monomer units of the formula I being from 1 to 100 mol %, the proportion of monomer units of the formula II being from 0 to 99 mol %, the proportion of monomer units of the formula III being from 0 to 99 mol % and the proportion of monomer units of the formula IV being from 0 to 75 mol %, each percentage being based on the polymer, and the average molecular weight of the polymer being from 1,000 to 100,000. .Iaddend.