Fused 6,6,6-membered heterocyclic electroactive polymers

Claim 2

A p-type electroactive polymer which comprises a charge polymer backbone of recurring units of a fused 6,6,6-membered unsaturated heterocyclic ring system wherein 6,6,6-membered unsaturated heterocyclic ring system connects into the polymer backbone through bonding in the outer carbocyclic rings, the central 6-member ring contains two heteroatoms para to each other, said heteroatoms selected from the group consisting of O, S, N, and substituted N, and a sufficient concentration of a charge-compensating anionic conductivity modifier associated therewith, wherein the polymer backbone is capable of undergoing reversible oxidation to form said charged polymer backbone.

Claim 3

The electroactive polymer according to claim 1 wherein the recurring units are selected from the group consisting of phenoxazine; N-alkyl phenoxazine; phenothiozine, thianthrene; phenoxathiin; dialkyldihydrophenazine; dihydrophenazine; dibenzodiozin; substituted derivatives thereof, wherin said substituted derivatives thereof are said recurring units substituted with from 1 to 3 substituents on the outer carbocyclic rings independently selected from H; disubstituted amino; alkyl of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms; alkylthio of 1 to 4 carbon atoms; a cycloaliphatic group of 5 or 6 carbon atoms; an aryl group of 6 to 10 carbon atoms; an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, an alkylthio of 1 to 4 carbon atoms; and a 5- or 6-membered nitrogen-containing unsaturated heterocyclic ring; and mixtures thereof.

Claim 4

The electroactive polymer according to claim 2 wherein the recurring units are linked into the polymer chain in the 2,7; 2,8; 3,7; or 3,8 positions.

Claim 5

The electroactive polymer according to claim 3 wherein the charge-compensating ionic dopant is an anion selected from the group consisting of AsF 4 - , AsF 6 - , ClO 4 - , PF 6 - , SO 3 CF 3 - , BF 4 - , NO 3 - , POF 4 - , CN - , SiF 5 - , SbCl 6 - , SbF 6 - , HSO 4 - , acetate, benzoate, tosylate, or mixtures thereof.

Claim 6

The electroactive polymer according to claim 3 wherein the recurring units are interspersed with connecting units, said connecting unit is selected from the group consisting of ##STR15## wherein R 1 is lower alkyl C 1 -C 6 , and cyclo alkyl, and R v , R vi and R vii are H, methyl, methoxy, halogen, and mixtures thereof.

Claim 7

The electroactive polymer according to claim 5 wherein the fused 6,6,6-membered heterocyclic recurring units are interspersed with connecting units selected from the group consisting of phenylene, dithiophenylene --CH═CH--, biphenylene, dithiobiphenylene, and ##STR16## or mixtures thereof.

Claim 8

The electroactive polymer according to claim 6 or 3 wherein the recurring unit is phenoxathiin.

Claim 9

The electroactive polymer according to claim 7 wherein the polymer is poly 3,7-(phenoxathiin-4,4'-dithiobiphenylene) plus a charge compensating anionic dopant.

Claim 10

The electroactive polymer according to claim 6 or 3 wherein the recurring unit is phenothiazine.

Claim 11

The electroactive polymer according to claim 9 wherein the polymer is poly 3,7-(N-methyl phenothiazine-2,5-oxadiazole) plus a charge compensating anionic dopant.

Claim 12

The electroactive polymer according to claim 10 or 3 wherein the charge-compensating ionic dopant is an anion selected from the group consisting of AsF 4 - , AsF 6 - , ClO 4 - , PF 6 - , SO 3 CF 3 - , BF 4 - , NO 3 - , POF 4 - , CN - , SiF 5 - , SbCl 6 - , SbF 6 - , HSO 4 - , acetate, benzoate, tosylate, or mixtures thereof.

Claim 13

A p-type electroactive polymer which comprises a charged polymer backbone and charge-compensating ionicdopants associated therewith of the formula: --R--X'--.sub.a --R'--.sub.c --Y'--.sub.b --.sub.n .sup.(+Sd) [M.sup.-S ].sub.d wherein a is 0 or 1; b is 0 or 1; c is 0 or 1; n is an integer from 1 to 1,000; d is an integer from 1 to 2,000; s is an integer 1, 2, or 3; R is a fused 6,6,6-membered unsaturated diradical-heterocyclic ring system wherein two heteroatoms are para in the central 6-membered ring and the heteroatoms are selected from the group consisting of O, S, N, N--R 1 wherein R 1 is lower alkyl C 1 -C 6 , aryl and cycloalkyl; R' is the same as R or a different fused 6,6,6-membered unsaturated heterocyclic ring system; X' is a connecting unit; Y' is the same connecting unit as X' or a different connecting unit; and M is a charge-compensating anionic dopant of opposite electrical charge to the charge of the polymer backbone wherein an X' or Y' connecting unit is selected from the group consisting of: ##STR17## wherein R 1 is lower alkyl C 1 --C 6 , aryl and cyclo alkyl, and R v , R vi and R vii are H, methyl, methoxy, halogen and mixtures thereof.

Claim 14

A p-type electroactive polymer which comprises a charged polymer backbone and charge-compensating ionicdopants associated therewith of the formula: --R--X'--.sub.a --R'--.sub.c --Y'--.sub.b --.sub.n .sup.(+Sd) [M.sup.-S ].sub.d wherein a is 0 or 1; b is 0 or 1; c is 0 or 1; n is an integer from 1 to 1,000; d is an integer from 1 to 2,000; s is an integer 1, 2, or 3; R is a fused 6,6,6-membered unsaturated diradical-heterocyclic ring system wherein two heteroatoms are para in the central 6-membered ring and the heteroatoms are selected from the group consisting of O, S, N, N--R 1 wherein R 1 is lower alkyl C 1 -C 6 , aryl and cycloalkyl; R' is the same as R or a different fused 6,6,6-membered unsaturated heterocyclic ring system; X' is a connecting unit; Y' is the same connecting unit as X' or a different connecting unit; and M is a charge-compensating anionic dopant of opposite electrical charge to the charge of the polymer backbone wherein an X' or Y' connecting unit is selected from the group consisting of: ##STR17## wherein R 1 is lower alkyl C 1 --C 6 , aryl and cyclo alkyl, and R v , R vi and R vii are H, methyl, methoxy, halogen and mixtures thereof.

Claim 15

The electroactive polymer according to claim 12 wherein R and R' are diradicals of the formula: ##STR18## wherein X and Y are independently selected from the group consisting of substituted N, O, S, N--R 1 ; wherein R 1 is lower alkyl C 1 -C 6 , areyl, cyclo alkyl; R ii and R iii are from one to three substituent groups independently selected from H; disubstituted amino; alkyl of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms; an alkylthio of 1 to 4 carbon atoms; a cycloaliphatic group of 5 to 6 carbon atoms; an aryl group of 6 to 10 carbon atoms; an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, an alkylthiol 1 to 4 carbon atoms; a 5- or 6-member nitrogen-containing unsaturated heterocyclic group.

Claim 16

The electroactive polymer according to claim 13 wherein a, b and c are zero, and the polymer has the formula: --R--.sub.n.sup.(+Sd) [M.sup.-S ].sub.d

Claim 17

The electroactive polymer according to claim 12 or 13 wherein a is 1, b and c are zero, and the polymer has the formula: --R--X'--.sub.n.sup.(+Sd) [M.sup.-S ].sub.d

Claim 18

The electroactive polymer according to claim 15 wherein X and Y are O and S for the diradical R.

Claim 19

The electroactive polymer according to claim 15 where X and Y are N--R 1 and S for the diradical R.

Claim 20

The electroactive polymer according to claim 17 wherein X is S, Y is N--R 1 , and R 1 is CH 3 for the diradical R and X' is ##STR19## and the polymer has the formula: ##STR20##

Claim 21

The electroactive polymer according to claim 18 wherein the charge-compensating ionic dopant M is an anion selected from the group consisting of AsF 4 - , AsF 6 - , ClO 4 - , PF 6 - , SO 3 CF 3 - , BF 4 - , NO 3 - , POF 4 - , CN - , SiF 5 - , SbCl 6 - , SbF 6 - , HSO 4 - , acetate, benzoate, tosylate, F - , Cl - , or mixtures thereof.

Claim 22

The polymer poly-3,7-(N-methylphenothiazine)-2,5-(1,3,4-oxadiazole).

Claim 23

The polymer poly-3,7-(N-methylphenothiazine)-2,5-(1,3,4-oxadiazole).