Soluble, electrically conductive polymers, process for preparing them, and their use

Claim 2

An intrinsically electrically conductive polymer having 3 to 10 structural units structural units which are mutually linked in the 2-position and/or 5-position and are comprised, as a statistical mean, of 60 to 100% by weight of structural units which are derived from at least one monomer of the formula (I) ##STR10## in which R 1 is a C 1 -C 12 -alkoxy group or --O(CH 2 CH 2 O) n CH 3 with n=1 to 4 and R 2 is a hydrogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group or --O(CH 2 CH 2 O) n CH 3 with n=1 to 4, or R 1 and R 2 together are --O(CH 2 ) m --CH 2 or --O(CH 2 ) m --O-- with m=1 to 12, of 0 to 40% by weight of structural units which are derived from at least one monomer of the formula (II) ##STR11## in which R 4 and R 5 independently of one another are a hydrogen atom, a halogen atom, a C 1 -C 12 -alkyl group or aryl or, together with the carbon atoms linking them, form an aromatic ring, R 3 and R 6 independently of one another are a hydrogen atom or R 3 together with R 4 and the carbon atoms linking them or R 5 together with R 6 and the carbon atoms linking them in each case form an aromatic ring, and X is an oxygen atom, a sulfur atom, an ═NH group, an ═N-alkyl group or an ═N-aryl group, of 0 to 40% by weight of structural units which are derived from at least one monomer of the formula (III) ##STR12## in which R 7 , R 8 , R 9 and R 10 independently of one another are a hydrogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group or an aryl group, Y and Z independently of one another are an oxygen atom, a sulfur atom, an ═NH group, an ═N-alkyl group or an ═N-aryl group and R 11 is an arylene group, a heteroarylene group or a conjugated system of the formula (CH═CH) o , where o is zero, 1, 2 or 3, and of 0 to 40% by weight of structural units which are derived from at least one monomer of the formula (IV) ##STR13## in which R 12 and R 13 independently of one another are a hydrogen atom, a halogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group, a C 1 -C 4 -alkylamino group or a C 1 -C 4 -acylamino group, R 14 is a halogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group, a C 1 -C 4 -alkylamino group or a C 1 -C 4 -acyl-amino group and X is as defined above, the polymer in the oxidized form being completely soluble in dipolar aprotic solvents or solvent mixtures at 25° C., solutions with a content of at lest 0.1 g of polymer in 100 ml of solvent being obtained at 25° C., said solvents or solvent mixtures having a δ p value greater than 3.5 (cal/ccm) 1/2 and a Hansen δ H value less than 6.5 (cal/ccm) 1/2 .

Claim 3

An intrinsically electrically conductive polymer as claimed in claim 1, wherein at least one of the two end groups consist of a structural unit which is derived from a compound of the formula (IV) ##STR14## in which R 12 and R 13 independently of one another are a hydrogen atom, a halogen atom, a C 1 -C 12 -alkyl group or a C 1 -C 12 -alkoxy group and R 14 is a halogen atom, a C 1 -C 12 -alkyl group or a C 1 -C 12 -alkoxy group and X is as defined in claim 1.

Claim 4

An intrinsically electrically conductive polymer as claimed in claim 1, wherein, in the formula (I), R 1 is OCH 3 or OC 2 H 5 and R 2 is H.

Claim 5

An intrinsically electrically conductive polymer as claimed in claim 1, from which solutions with a concentration of at least 1.0 g of polymer in 100 ml of a dipolar aprotic solvent can be prepared at 25° C.

Claim 6

An intrinsically electrically conductive polymer as claimed in claim 1, which has an electrical conductivity of 10 -4 to 100 S/cm.

Claim 7

An intrinsically electrically conductive polymer as claimed in claim 1, dissolved in a dipolar aprotic solvent, wherein the dipolar aprotic solvent is acetone, acetonitrile, gamma-butyrolactone, epsilon-caprolactam, crotonaldehyde, methyl cyanoacetate, N-methylformamide, N,N-dimethyl formamide, dimethylsulfoxide, diethylsulfate, furfural, nitropropane, propionitrile, triethyl phosphate, 3-methoxypropionitrile, N-methylpyrrolidone, nitrobenzene, nitromethane, propylene carbonate, sulfolan, liquified or dissolved sulfur dioxide, or mixtures thereof, with each other or with non-solvents.

Claim 8

An electrically conductive coating composition comprising at least about 0.1 g of an intrinsically electrically conductive polymer of claim 1 dissolved in each 100 ml of solvent, said solvent comprising a dipolar aprotic solvent.

Claim 9

A coating composition as claimed in claim 1, wherein said solution contains at least about 1 g of said polymer per 100 ml of solvent, and wherein said solvent comprises acetonitrile, acrylonitrile, benzonitrile, gamma-butyrolactone, diethylsulfate, furfural, N-methylpyrrolidone, nitromethane, nitropropane, propionitrile, propylene carbonate, or liquified or dissolved sulfur dioxide.

Claim 10

An electrically non-conductive material coated with a coating composition of claim 8.

Claim 11

An electrically non-conductive film or fiber coated with a coating composition of claim 8.

Claim 12

An intrinsically electrically conductive polymer as claimed in claim 1, wherein said solvents or solvent mixtures have a δ p value greater than 5.5 (cal/ccm) 1/2 and a Hansen δ H value less than 5.0 (cal/ccm) 1/2 .

Claim 13

An intrinsically electrically conductive polymer having 3 to 10 structural units which are mutually linked in the 2-position and/or 5-position and are comprised, as a statistical mean, of 50 to 100% by weight of structural units which are derived from at least one monomer of the formula (I) ##STR15## in which R 1 is a C 1 -C 12 -alkoxy group or --O(CH 2 CH 2 O) n CH 3 with n=1 to 4 and R 2 is a hydrogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group or --O(CH 2 CH 2 O) n CH 3 with n=1 to 4, or R 1 and R 2 together are --O(CH 2 ) m --CH 2 or --O(CH 2 ) m --O-- with m=1 to 12. of 0 to 40% by weight of structural units which are derived from at least one monomer of the formula (II) ##STR16## in which R 4 and R 5 independently of one another are a hydrogen atom, a halogen atom, a C 1 -C 12 -alkyl group or aryl or, together with the carbon atoms linking them, form an aromatic ring, R 3 and R 6 independently of one another are a hydrogen atom or R 3 together with R 4 and the carbon atoms linking them or R 5 together with R 6 and the carbon atoms linking them in each case form an aromatic ring, and X is an oxygen atom, a sulfur atom, an ═NH group, an ═N-alkyl group or an ═N-aryl group, of 0 to 40% by weight of structural units which are derived from at least one monomer of the formula (III) ##STR17## in which R 7 , R 8 , R 9 and R 10 independently of one another are a hydrogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group or an aryl group, Y and Z independently of one another are an oxygen atom, a sulfur atom, an ═NH group, an ═N-alkyl group or an ═N-aryl group and R 11 is an arylene group, a heteroarylene group or a conjugated system of the formula (CH═CH) o , where o is zero, 1, 2 or 3, and of up to 40% by weight of structural units which are derived from at least one monomer of the formula (IV) ##STR18## in which R 12 and R 13 independently of one another are a hydrogen atom, a halogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group, a C 1 -C 4 -alkylamino group or a C 1 -C 4 -acylamino group, R 14 is a halogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group, a C 1 -C 4 -alkylamino group or a C 1 -C 4 -acylamino group and X is as defined above, the end groups of said intrinsically electrically conductive polymer being structural units derived from a monomer of said formula (IV), the polymer in the oxidized form being completely soluble in dipolar aprotic solvents or solvent mixtures at 25° C., solutions with a content of at least 0.1 g of polymer in 100 ml of solvent being obtained at 25° C., said solvents or solvent mixtures having a δ p value greater than 3. 5(cal/ccm) 1/2 and a Hansen δ H value less than 6.5 (cal/ccm) 1/2 .

Claim 14

An intrinsically electrically conductive polymer having 3 to 10 structural units which are mutually linked in the 2-position and/or 5-position and are comprised, as a statistical mean, of 50 to 100% by weight of structural units which are derived from at least one monomer of the formula (I) ##STR15## in which R 1 is a C 1 -C 12 -alkoxy group or --O(CH 2 CH 2 O) n CH 3 with n=1 to 4 and R 2 is a hydrogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group or --O(CH 2 CH 2 O) n CH 3 with n=1 to 4, or R 1 and R 2 together are --O(CH 2 ) m --CH 2 or --O(CH 2 ) m --O-- with m=1 to 12. of 0 to 40% by weight of structural units which are derived from at least one monomer of the formula (II) ##STR16## in which R 4 and R 5 independently of one another are a hydrogen atom, a halogen atom, a C 1 -C 12 -alkyl group or aryl or, together with the carbon atoms linking them, form an aromatic ring, R 3 and R 6 independently of one another are a hydrogen atom or R 3 together with R 4 and the carbon atoms linking them or R 5 together with R 6 and the carbon atoms linking them in each case form an aromatic ring, and X is an oxygen atom, a sulfur atom, an ═NH group, an ═N-alkyl group or an ═N-aryl group, of 0 to 40% by weight of structural units which are derived from at least one monomer of the formula (III) ##STR17## in which R 7 , R 8 , R 9 and R 10 independently of one another are a hydrogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group or an aryl group, Y and Z independently of one another are an oxygen atom, a sulfur atom, an ═NH group, an ═N-alkyl group or an ═N-aryl group and R 11 is an arylene group, a heteroarylene group or a conjugated system of the formula (CH═CH) o , where o is zero, 1, 2 or 3, and of up to 40% by weight of structural units which are derived from at least one monomer of the formula (IV) ##STR18## in which R 12 and R 13 independently of one another are a hydrogen atom, a halogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group, a C 1 -C 4 -alkylamino group or a C 1 -C 4 -acylamino group, R 14 is a halogen atom, a C 1 -C 12 -alkyl group, a C 1 -C 12 -alkoxy group, a C 1 -C 4 -alkylamino group or a C 1 -C 4 -acylamino group and X is as defined above, the end groups of said intrinsically electrically conductive polymer being structural units derived from a monomer of said formula (IV), the polymer in the oxidized form being completely soluble in dipolar aprotic solvents or solvent mixtures at 25° C., solutions with a content of at least 0.1 g of polymer in 100 ml of solvent being obtained at 25° C., said solvents or solvent mixtures having a δ p value greater than 3. 5(cal/ccm) 1/2 and a Hansen δ H value less than 6.5 (cal/ccm) 1/2 .