Thermally stable forms of electrically conductive polyaniline

What is claimed is:

1. A thermally stable electrically conductive homopolymer or copolymer comprising a substituted or unsubstituted polyaniline derived from polymerizing an aniline of the formula: ##STR5## having therein a dopant solute selected from the group consisting of: ##STR6## in an amount sufficient to provide a doped polyaniline having a conductivity of at least about 10.sup.-6 ohm.sup.-1 cm.sup.-1 wherein:

R.sub.1 is the same or different at each occurrence and is a substituted or unsubstituted organic radical, amino, alkylamino, dialkylamino, arylamino, diarylamino, or alkylarylamino;

n is an integer from 0 to 4;

m is an integer from 1 to 5 with the proviso that the sum of n and m is 5;

r is an integer equal to or greater than 1;

R.sub.2 and R.sub.4 are the same or different at each occurrence and are R.sub.3 substituents, hydrogen or alkyl; with the proviso that at least one of R.sub.2 or R.sub.4 is hydrogen and with the further proviso that R.sub.2 and R.sub.4 are not alkylsulfonyl, arylsulfonyl or alkanoyl;

R.sub.3 is deuterium, alkyl, alkenyl, alkoxy, cycloalkyl, hydroxy, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl, arylthio, arylsulfinyl, alkoxycarbonyl, alkylsilane, phosphinic acid, arylsulfonyl, phosphonic acid, sulfonic acid, boric acid, phosphoric acid, sulfonate, borate, phosphonate, phosphinate, phosphate, sulfinic acid, sulfinate, carboxylic acid, halo, carboxylate, cyano, or alkyl or alkoxy substituted with one or more phosphonic acid, sulfonic acid, boric acid, sulfinic acid, sulfinate, phosphoric acid, sulfonate, borate, carboxylate, phosphonate, phosphate, carboxylic acid, halo, hydroxy, cyano or epoxy moieties; or any two R.sub.3 substituents or any one R.sub.3 substituent and any one R.sub.2 or R.sub.4 substituent taken together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic carbon ring, or any two R.sub.3 substituents or any one R.sub.3 substitutent and any one R.sub.2 or R.sub.4 substituent taken together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic carbon ring which includes one or more divalent ester, carbonyl, nitrogen, sulfur, sulfinyl, sulfonyl or oxygen, or R.sub.3 is an aliphatic moiety having repeat units of the formula:

wherein q is a positive whole number; with the proviso that the homopolymer or copolymer includes 10 or more recurring aromatic moieties.

2. The homopolymer or copolymer according to claim 1 wherein said homopolymer or copolymer is of the formula: ##STR7## wherein: x is an integer equal to or greater than 1;

y is equal to or greater than 1, with the proviso that the ratio of x to y is greater than about 0.5;

z, v and u are the same or different and are equal to or greater than about 1;

n is an integer from 0 to 4;

m is an integer from 1 to 5 with the proviso that the sum of n and m is 5;

R.sub.2 and R.sub.4 are the same or different at each occurrence and are R.sub.3 substituents, hydrogen or alkyl;

R.sub.3 is the same or different at each occurrence and is alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl, arylthio, arylsulfinyl, alkoxycarbonyl, phosphinic acid, phosphonic acid, alkylsilane, boric acid, arylsufonyl, carboxylic acid, halo, hydroxy, phosphate, sulfonate, phosphonate, borate, phosphinate, carboxylate, cyano, sulfonic acid, phosphoric acid or alkyl or alkoxy substituted with one or more sulfonic acid, carboxylic acid, sulfinate, phosphoric acid, boric acid, sulfinic acid, halo, cyano, epoxy, hydroxy, sulfonate, phosphate, phosphonate, phosphinic acid, phosphinate, carboxylate, phosphonic acid or borate moieties; or any two R.sub.3 substituents or any one R.sub.3 group and any R.sub.2 or R.sub.4 group together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic carbon ring or any two R.sub.3 substituents or any one R.sub.3 substituent and any one R.sub.2 or R.sub.4 substituent taken together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic carbon ring which includes one or more divalent nitrogen, ester, carbonyl, sulfur, sulfinyl, sulfonyl, or oxygen.

3. The homopolymer or copolymer according to claim 1 wherein m is from about 3 to about 5.

4. The homopolymer or copolymer according to claim 3 wherein m is from about 4 to about 5.

5. The homopolymer or copolymer according to claim 1 wherein said polyaniline is derived from substituted anilines.

6. The homopolymer or copolymer according to claim 1 wherein said polyaniline is derived from unsubstituted aniline.

7. The homopolymer or copolymer according to claim 2 wherein R.sub.3 is the same or different at each occurrence and is alkyl or alkoxy having from 1 to about 30 carbon atoms, cyano, halo, hydroxy, or alkyl or alkoxy substituted with carboxylic acid, phosphoric acid, phosphinic acid, phosphinate, boric acid, carboxylate, sulfinic acid, sulfonic acid, sulfonate, sulfinate, phosphonate, phosphate, phosphoric acid or borate substituents.

8. The homopolymer or copolymer according to claim 7 wherein R.sub.3 is the same or different at each occurrence and is alkyl or alkoxy having from 1 to about 20 carbon atoms, or substituted alkyl or alkoxy having from 1 to about 20 carbon atoms wherein permissible substituents are alkyl, carboxylic acid, sulfonic acid, phosphoric acid, boric acid, sulfinate, sulfonate, phosphonate, phosphate, carboxylate, phosphonic acid or borate substituents.

9. The homopolymer or copolymer according to claim 8 wherein R.sub.3 is the same or different at each occurrence and is alkyl having from 1 to about 4 carbon atoms.

10. The homopolymer or copolymer according to claim 7 wherein n is 0, 1, 2, 3 or 4.

11. The homopolymer or copolymer according to claim 10 wherein n is 0, 1, 2 or 3.

12. The homopolymer or copolymer according to claim 11 wherein n is 0 or 1.

13. The homopolymer or copolymer according to claim 2 wherein R.sub.3 is alkoxy, alkyl, halo, phenyl, haloalkyl, perhaloalkyl, cyano, or alkoxy, alkyl or phenyl substituted with one or more alkoxy, sulfonic acid, carboxylic acid, boric acid, phosphoric acid, hydroxy, fluoro, cyano, sulfinic acid, carboxylate, sulfonate, sulfinate, phosphonate, phosphate, phosphoric acid or borate or an aliphatic moiety of the formula:

wherein q is a positive whole number.

14. The homopolymer or copolymer according to claim 13 wherein:

R.sub.3 is fluoro, or substituted or unsubstituted alkyl, alkoxy or phenyl wherein permissible substituents are one or more fluoro, sulfonic acid, phosphoric acid, sulfinic acid, phosphonate, phosphate, sulfonate, borate, phosphonic acid, boric acid, carboxylic acid, carboxylate, hydroxy or cyano.

15. The homopolymer or copolymer according to claim 14 wherein:

R.sub.3 is fluoro, alkyl or alkyl or alkoxy substituted with one or more carboxylic acid, sulfonic acid, phosphonate, carboxylate, phosphate, sulfonate, borate, sulfinic acid, sulfinate, phosphonic acid, phosphoric acid, boric acid, fluoro or nitro substituents wherein the aliphatic moiety contains from about 1 to about 30 carbon atoms, or R.sub.3 phenyl or phenyl substituted with one or more substituents selected from the group consisting of fluoro, alkyl or alkyl substituted with one or more fluoro, cyano, carboxylic, sulfonic, borate, carboxylate, sulfinic acid, sulfinate, sulfonate, phosphate, phosphoric acid or boric acid moieties.

16. The homopolymer or copolymer of claim 1 wherein R.sub.1 is alkyl or substituted alkyl.

17. The homopolymer or copolymer according to claim 1 wherein said dopant is a compound of the formula: ##STR8## wherein: M is H.sup.+, a metal cation or non-metal cation;

c is 0, 1, 2, 3 or 4;

e is 0, 1 or 2;

f is 0, 1 or 2;

g is 0, 1 or 2;

d is 0, 1 or 2; and

R.sub.6 is hydroxy, alkyl, halo, cyano, phosphonic acid, phosphonate, phosphinic acid, phosphinate, alkoxy, hydroxy, sulfinic acid, sulfinate, or substituted or unsubstituted aryl or alkyl having from 1 to about 30 carbon atoms wherein permissible substituents are perhaloalkyl, halo, cyano, phosphonate, borate, phosphonic acid, sulfonate, carboxylate, phosphate, haloalkyl, sulfonic acid, sulfinic acid, sulfinate, phosphoric acid, boric acid, carboxylic acid, or any two R.sub.6 substituents together may form an alkenylene chain completing a fused aromatic ring system, which chain may be unsubstituted or substituted with one or more halo, hydroxy, phosphonate, borate, phosphonic acid, sulfonate, phosphate, boric acid, phosphoric acid, carboxylate, cyano, sulfonic acid or carboxylic acid groups, or R.sub.6 is an aliphatic moiety of the formula:

wherein q is 1 to about 10.

18. The homopolymer or copolymer according to claim 17 wherein said dopant is a compound of the formula: ##STR9## wherein: M is H.sup.+ ;

c is 1, 2 or 3;

d and e are the same or different and are 0, 1 or 2; and

R.sub.6 is hydroxy, cyano, halo or substituted or unsubstituted alkyl having from 1 to about 30 carbon atoms phenyl or phenylalkyl having from 7 to about 30 carbon atoms wherein permissible substituents are halo, alkyl, alkoxy, cyano, boric acid, phosphoric acid, phosphate, borate, phosphonate, sulfonate, phosphonic acid, sulfonic acid, carboxylate and carboxylic acid groups or any two R.sub.6 groups may form a divalent substituted or unsubstituted alkenylene chain completing a naphthalene, anthracene or phenanthraene-fused ring structure, which chain may be substituted with one or more hydroxy, cyano, halo, sulfonic acid, boric acid, phosphoric acid, alkyl, alkoxy, sulfinate, phosphate, borate, phosphonate, carboxylate, phosphonic acid, phosphonate, sulfonate, boric acid, borate, sulfinic acid, phosphoric acid, phosphate, sulfonate, phosphonic acid, carboxylic acid or alkyl substituted with one or more carboxylic acid, sulfonic acid or fluoro groups.

19. The homopolymer or copolymer according to claim 18 wherein:

M is H.sup.+ ;

c is 1, 2 or 3;

d and e are the same or different and are 0, 1 or 2; and

R.sub.6 is alkyl having from 1 to about 15 carbon atoms, fluoro, alkyl substituted with one or more fluoro, cyano, boric acid, phosphoric acid, phosphate, carboxylate, borate, phosphonate, sulfonate, sulfinic acid, sulfinate, phosphonic acid, sulfonate, sulfonic acid or carboxylic acid group; or any two R.sub.5 groups together may form a substituted or unsubstituted divalent alkenylene chain completing a naphthalene, anthracene or phenanthrene structure where permissible substituents are one or more sulfonic acid, boric acid, phosphoric acid, phosphate, borate, sulfinic acid, sulfinate, phosphonate, carboxylate, sulfonate, phosphonic acid, fluoro, carboxylic acid, or alkyl substituted with one or more fluoro, sulfonic acid, carboxylate, phosphonic acid, phosphonate, sulfonate, boric acid, borate, phosphoric acid, phosphate, or carboxylic acid groups.

20. The homopolymer or copolymer according to claim 18 wherein:

M is H.sup.+ ;

c is 1, 2 or 3;

d is 0;

e is 0, 1 or 2; and

R.sub.6 is alkyl, fluoro or alkyl substituted with one or more fluoro substituents or any two R.sub.5 group together may form a substituted or unsubstituted divalent alkenylene chain completing a naphthalene, anthracene or phenanthracene ring structure, wherein permissible substituents are one or more sulfonic acid, fluoro or alkyl substituted with one or more sulfonic acid or fluoro groups.

21. The homopolymer or copolymer according to claim 2 wherein z is equal to or greater than about 5.

22. The homopolymer or copolymer according to claim 21 wherein z is equal to or greater than about 10.

23. The homopolymer or copolymer according to claim 22 wherein said polyaniline is of the Formulas III or V.

24. The homopolymer or copolymer according to claim 23 wherein x is equal to or greater than about 2, with the proviso that the ratio of x to y is at least about 2.

25. The homopolymer or copolymer according to claim 24 wherein x is from about 4 to about 8 and y is from about 0 to about 2, with the proviso that the ratio of x to y is at least about 2.

26. The homopolymer or copolymer according to claim 25 wherein x is 4 and y is 2.

27. The homopolymer or copolymer according to claim 1 wherein said polymers contain sufficient dopant to provide a doped polyaniline having a conductivity of at least about 10.sup.-6 ohm.sup.-1 cm.sup.-1.

28. The homopolymer or copolymer according to claim 1 wherein said conductivity is at least about 10.sup.-3 ohm.sup.-1 cm.sup.-1.

29. The homopolymer or copolymer according to claim 28 wherein said conductivity is at least about 10.sup.-2 ohm.sup.-1 cm.sup.-1.

30. The homopolymer or copolymer according to claim 29 wherein said conductivity is at least about 10.sup.-2 ohm.sup.-1 cm.sup.-1.

31. The homopolymer or copolymer according to claim 30 wherein said conductivity is at least about 10.sup.-1 ohm.sup.-1 cm.sup.-1.

32. The homopolymer or copolymer according to claim 31 wherein said conductivity is at least about 10.sup.0 ohm.sup.-1 cm.sup.-1.

33. The homopolymer or copolymer according to claim 1 wherein R.sub.2 and R.sub.4 are hydrogen or alkyl.

34. The homopolymer or copolymer according to claim 33 wherein R.sub.2 and R.sub.4 are hydrogen.

35. The homopolymer or copolymer according to claim 34 wherein m is 5 and n is 0.

36. The homopolymer or copolymer according to claim 1 wherein:

R.sub.2 and R.sub.4 are hydrogen;

n is 0; and

m is 4;

and wherein said dopant soluble is of the formula: ##STR10## wherein: R.sub.6 is alkyl having from 1 to about 30 carbon atoms.

37. The homopolymer or copolymer according to claim 36 wherein:

R.sub.6 is alkyl having from 1 to about 10 carbon atoms.

38. The homopolymer or copolymer according to claim 37 wherein R.sub.6 is methyl substituted of the para position.

39. The homopolymer or copolymer according to claim 38 wherein R.sub.6 is dodecyl substituted of the para position.

40. A thermally stable electrically conductive doped polyaniline comprising an ionized polyaniline backbone polymer and a dopant solute species selected from the group consisting of: ##STR11## wherein R.sub.1 is a substituted or unsubstituted organic radical; and r is a positive whole number equal to or greater than 1.

41. A polyaniline according to claim 40 wherein said homopolymer or copolymer comprises recurring units selected from the group consisting of moieties of the formula: ##STR12## wherein: x is an integer equal to or greater than 1;

y is equal to or greater than 1, with the proviso that the ratio of x to y is greater than about 0.5;

z, v and u are the same or different and are equal to or greater than about 1;

n is an integer from 0 to 4;

m is an integer from 1 to 5 with the proviso that the sum of n and m is 5;

R.sub.2 and R.sub.4 are the same or different at each occurrence and are R.sub.3 substituents, hydrogen or alkyl with the proviso that at least one of R.sub.2 or R.sub.4 is hydrogen and with the further proviso that R.sub.2 and R.sub.4 are not alkylsulfoyl, arylsulfonyl or alkanoyl;

R.sub.3 is the same or different at each occurrence and is alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl, arylthio, arylsulfinyl, alkoxycarbonyl, phosphinic acid, phosphonic acid, alkylsilyl, boric acid, arylsufonyl, carboxylic acid, halo, hydroxy, phosphate, sulfonate, phosphonate, borate, phosphinate, carboxylate, cyano, sulfonic acid, phosphoric acid or alkyl or alkoxy substituted with one or more sulfonic acid, carboxylic acid, sulfinate, phosphoric acid, boric acid, sulfinic acid, halo, cyano, epoxy, hydroxy, sulfonate, phosphate, phosphonate, phosphinic acid, phosphinate, carboxylate, phosphonic acid or borate moieties; or any two R.sub.3 substituents or any one R.sub.3 group and any R.sub.2 or R.sub.4 group together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic carbon ring, or any two Z is equal to or greater than 1 alkenylene chain completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic carbon ring which includes one or more divalent nitrogen, ester, carbonyl, sulfur, sulfinyl, sulfonyl or oxygen.

42. A polyaniline according to claim 40 wherein m is about 3 to about 5.

43. A polyaniline according to claim 42 wherein m is from about 4 to about 5.

44. A polyaniline according to claim 40 wherein said polyaniline is derived from substituted anilines.

45. A polyaniline according to claim 40 wherein said polyaniline is derived from unsubstituted aniline.

46. A polyaniline according to claim 41 wherein R.sub.3 is the same or different at each occurrence and is alkyl or alkoxy having from 1 to about 30 carbon atoms, cyano, halo, hydroxy, or alkyl or alkoxy substituted with carboxylic acid, phosphoric acid, phosphinic acid, phosphinate, boric acid, carboxylate, sulfinic acid, sulfonic acid, sulfonate, sulfinate, phosphonate, phosphate, phosphoric acid or borate substituents.

47. A polyaniline according to claim 46 wherein R.sub.3 is the same or different at each occurrence and is alkyl or alkoxy having from 1 to about 20 carbon atoms, or substituted alkyl or alkoxy having from 1 to about 20 carbon atoms wherein permissible substituents are alkyl, carboxylic acid, sulfonic acid, phosphoric acid, boric acid, sulfinate, sulfonate, phosphonate, phosphate, carboxylate, phosphonic acid or borate substituents.

48. A polyaniline according to claim 47 wherein R.sub.3 is the same or different at each occurrence and is alkyl having from 1 to about 4 carbon atoms.

49. A polyaniline according to claim 48 wherein n is 0, 1, 2, 3 or 4.

50. A polyaniline according to claim 49 wherein n is 0, 1, 2 or 3.

51. A polyaniline according to claim 50 wherein n is 0, or 1.

52. A polyaniline according to claim 41 wherein R.sub.3 is alkoxy, alkyl, halo, phenyl, haloalkyl, perhaloalkyl, cyano, or alkoxy, alkyl or phenyl substituted with one or more nitro, alkoxy, sulfonic acid, carboxylic acid, boric acid, phosphoric acid, hydroxy, fluoro, cyano, sulfinic acid, carboxylate, sulfonate, sulfinate, phosphonate, phosphate, phosphoric acid or borate or an aliphatic moiety of the formula:

wherein q is a positive whole number.

53. A polyaniline according to claim 52 wherein:

R.sub.3 is fluoro, or substituted or unsubstituted alkyl, alkoxy or phenyl wherein permissible substituents are one or more fluoro, sulfonic acid, phosphoric acid, sulfinic acid, phosphonate, phosphate, sulfonate, borate, phosphonic acid, boric acid, carboxylic acid, carboxylate, hydroxy or cyano.

54. A polyaniline according to claim 53 wherein:

R.sub.3 is fluoro, alkyl or alkyl or alkoxy substituted with one or more carboxylic acid, sulfonic acid, phosphonate, carboxylate, phosphate, sulfonate, borate, sulfinic acid, sulfinate, phosphonic acid, phosphoric acid, boric acid, fluoro or substituents wherein the aliphatic moiety contains from about 1 to about 30 carbon atoms, or R.sub.3 phenyl or phenyl substituted with one or more substituents selected from the group consisting of fluoro, alkyl or alkyl substituted with one or more fluoro, cyano, carboxylic, sulfonic, borate, carboxylate, sulfinic acid, sulfinate, sulfonate, phosphate, phosphoric acid or boric acid moieties.

55. A polyaniline of claim 40 wherein R.sub.1 is alkyl or substituted alkyl.

56. A polyaniline according to claim 40 wherein said dopant is a compound of the formula: ##STR13## wherein: M is H.sup.+, a metal cation or non-metal cation;

c is 0, 1, 2, 3 or 4;

e is 0, 1 or 2;

f is 0, 1 or 2;

g is 0, 1 or 2;

d is 0, 1 or 2; and

R.sub.6 is hydroxy, alkyl, halo, cyano, phosphonic acid, phosphonate, phosphinic acid, phosphinate, alkoxy, hydroxy, sulfinic acid, sulfinate, or substituted or unsubstituted aryl or alkyl having from 1 to about 30 carbon atoms wherein permissible substituents are perhaloalkyl, halo, cyano, phosphonate, borate, phosphonic acid, sulfonate, carboxylate, phosphate, haloalkyl, sulfonic acid, sulfinic acid, sulfinate, phosphoric acid, boric acid, carboxylic acid, or any two R.sub.6 substituents together may form an alkenylene chain completing a fused aromatic ring system, which chain may be unsubstituted or substituted with one or more halo, hydroxy, phosphonate, borate, phosphonic acid, sulfonate, phosphate, boric acid, phosphoric acid, carboxylate, cyano, sulfonic acid or carboxylic acid groups, or R.sub.6 is an aliphatic moiety of the formula:

wherein q is 1 to about 10.

57. A polyaniline according to claim 56 wherein said dopant is a compound of the formula: ##STR14## wherein: M is H.sup.+ ;

c is 1, 2 or 3;

d and e are the same or different and are 0, 1 or 2; and

R.sub.6 is hydroxy, cyano, halo or substituted or unsubstituted alkyl having from 1 to about 30 carbon atoms, phenyl or phenylalkyl having from 7 to about 30 carbon atoms wherein permissible substituents are halo, alkyl, alkoxy, cyano, boric acid, phosphoric acid, phosphate, borate, phosphonate, sulfonate, phosphonic acid, sulfonic acid, carboxylate and carboxylic acid groups or any two R.sub.6 groups may form a divalent substituted or unsubstituted alkenylene chain completing a naphthalene, anthracene or phenanthracene-fused ring structure, which chain may be substituted with one or more hydroxy, cyano, halo, sulfonic acid, boric acid, phosphoric acid, alkyl, alkoxy, sulfinate, phosphate, borate, phosphonate, carboxylate, phosphonic acid, phosphonate, sulfonate, boric acid, borate, sulfinic acid, phosphoric acid, phosphate, sulfonate, phosphonic acid, carboxylic acid or alkyl substituted with one or more carboxylic acid, sulfonic acid or fluoro groups.

58. A polyaniline according to claim 57 wherein:

M is H.sup.+ ;

c is 1, 2 or 3;

d and e are the same or different and are 0, 1 or 2; and

R.sub.6 is alkyl having from 1 to about 15 carbon atoms, fluoro, alkyl substituted with one or more fluoro, cyano, boric acid, phosphoric acid, phosphate, carboxylate, borate, phosphonate, sulfonate, sulfinic acid, sulfinate, phosphonic acid, sulfonate, sulfonic acid or carboxylic acid group; or any two R.sub.6 groups together may form a substituted or unsubstituted divalent alkenylene chain completing a naphthalene, anthracene or phenanthrene structure where permissible substituents are one or more sulfonic acid, boric acid, phosphoric acid, phosphate, borate, sulfinic acid, sulfinate, phosphonate, carboxylate, sulfonate, phosphonic acid, fluoro, carboxylic acid, or alkyl substituted with one or more fluoro, sulfonic acid, carboxylate, phosphonic acid, phosphonate, sulfonate, or carboxylic acid groups.

59. A polyaniline according to claim 57 wherein:

M is H.sup.+ ;

c is 1, 2 or 3;

d is 0;

e is 0, 1 or 2; and

R.sub.6 is alkyl, fluoro or alkyl substituted with one or more fluoro substituents or any two R.sub.5 groups together may form a substituted or unsubstituted divalent alkenylene chain completing a naphthalene, anthracene or phenanthracene ring structure, wherein permissible substituents are one or more sulfonic acid, fluoro or alkyl substituted with one or more sulfonic acid or fluoro groups.

60. A polyaniline according to claim 40 wherein said polyaniline contain sufficient dopant to provide a doped polyaniline having a conductivity of at least about 10.sup.-6 ohm.sup.-1 cm.sup.-1.

61. A polyaniline according to claim 60 wherein said conductivity is at least about 10.sup.-4 ohm.sup.-1 cm.sup.-1.

62. A polyaniline according to claim 61 wherein said conductivity is at least about 10.sup.-3 ohm.sup.-1 cm.sup.-1.

63. A polyaniline according to claim 62 wherein said conductivity is at least about 10.sup.-2 ohm.sup.-1 cm.sup.-1.

64. A polyaniline according to claim 63 wherein said conductivity is at least about 10.sup.-2 ohm.sup.-1 cm.sup.-1.

65. A polyaniline according to claim 64 wherein said conductivity is at least about 10.sup.-1 ohm.sup.-1 cm.sup.-1.

66. A polyaniline according to claim 65 wherein said conductivity is at least about 10.sup.0 ohm.sup.-1 cm.sup.-1.

67. A polyaniline according to claim 41 wherein R.sub.2 and R.sub.4 are hydrogen or alkyl.

68. A polyaniline according to claim 67 wherein R.sub.2 and R.sub.4 are hydrogen.

69. A polyaniline according to claim 68 wherein m is 5 and n is 0.

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BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to thermally stable electrically conductive substituted or unsubstituted polyanilines, and to compositions comprising such polyanilines and other non-electrically conductive polymers. Another aspect of this invention relates to a method of using such polyanilines and compositions to give conducting polymer articles, including films, fibers and coatings, and to fabricate such articles.

2. Prior Art

There has recently been an increased interest in the electrochemistry and electrical phenomena of polymeric systems. Recently, work has intensified with backbone polymers having extended conjugation in at least one backbone chain.

One conjugated polymer system currently under study is polyaniline. Kobayashi, Tetsuhiko, et al., J. Electroanal. Chem., "Electrochemical Reactions Concerned With Electrochromism of Polyaniline Film-Coated Electrodes", 177 (1984) 281-291, describes various experiments in which spectro electro-chemical measurement of a polyaniline film coated electrode were made. French Patent No. 1,519,729; French Patent of Addition 94,536; U.K. Patent 1,216,549; "Direct Current Conductivity of Polyaniline Sulfate", M. Donomedoff, F. Kautier-Cristojini, R. ReSur-vall, M. Jozefowicz, L-T. Yu, and R. Buvet, J. Chim. Phys. Physicohim. Brol 68, 1055 (1971); "Continuous Current Conductivity of Macromolecular Materials", L-T. Yu, M. Jozefowicz, and R. Buvet, Chim. Macromol. 1, 469 (1970); "Polyaniline Based Filmogenic Organic Conductive Polymers", D. LaBarre and M. Jozefowicz, C. R. Read. Sci., Ser. C, 269, 964 (1969); "Recently Discovered Properties of Semiconducting Polymers", M. Jozefowicz, L-T, Yu, J. Perichon, and R. Buvet, J. Polym. Sci., Part C, 22, 1187 (1967); "Electrochemical Properties of Polyaniline Sulfates", F. Cristojini, R. De Surville, and M. Jozefowicz, Cr. Read. Sci., Ser. C, 268, 1346 (1979); "Electrochemical Cells Using Protolytic Organic Semiconductors", R. De Surville, M. Jozefowicz, L-T. Yu, J. Perichon, R. Buvet, Electrochem. Ditn. 13, 1451 (1968); "Oligomers and Polymers Produced by Oxidation of Aromatic Amines", R. De Surville, M. Jozefowicz, and R. Buvet, Ann. Chem. (Paris), 2 5 (1967); "Experimental Study of the Direct Current Conductivity of Macromolecular Compounds" L-T. Yu, M. Borredon, M. Jozefowicz, G. Belorgey, and R. Buvet, J. Polym. Sci. Polym. Symp., 16, 2931 (1967); "Conductivity and Chemical Properties of Oligomeric Polyaniline", M. Jozefowicz, L-T. Yu, G. Belorgey, and R. Buvet, J. Polym. Sci., Polym. Symp., 16, 2934 (1967); "Products of the Catalytic Oxidation of Aromatic Amines", R. De Surville, M. Jozefowicz, and R. Buvet, Amm. Chem. (Paris), 2, 149 (1967); "Conductivity and Chemical Composition of Macromolecular Semiconductors", Rev. Gen. Electr., 75 1014 (1966); "Relation Between the Chemical and Electrochemical Properties of Macromolecular Semiconductors", M. Jozefowicz and L-T. Yu, Rev. Gen. Electr., 75 1008 (1966); "Preparation, Chemical Properties, and Electrical Conductivity of Poly-N-Alkyl Anilines in the Solid State", D. Muller and M. Jozefowicz, Bull. Soc. Chem. Fr. 4087 (1972).

U.S. Pat. Nos. 3,963,498 and 4,025,463 describe oligomeric polyanilines and substituted polyanilines having not more than 8 aniline repeat units which are described as being soluble in certain organic solvents and which are described as being useful in the formation of semi-conductors compositions having bulk electrical conductivities up to about 7.times.10.sup.-3 S/cm and, surface resistivities of 4.times.10.sup.7 ohm/square. European Patent No. 0017717 is an apparent improvement in the compositions of U.S. Pat. Nos. 3,963,498 and 4,025,463 and states that the polyaniline can be formed into a latex composite through use of acetone solutions of the oligomers of polyaniline and a suitable binder polymer.

In the general field of conducting polymers, it was heretofore neither demonstrated nor conceived that thermally stable conductive polyanilines could be prepared, and that compositions comprising such polyanilines and one or more thermoplastic polymers could be fabricated into useful articles by melt blending techniques. Thus, a need exists for thermally stable electrically conductive polyanilines and for techniques to facilitate the fabrication of shaped conductive polyaniline articles, especially articles such as films, sheets, fibers, prismatic objects and coatings.

SUMMARY OF THE INVENTION

One aspect of the present invention relates to a thermally stable, electrically conductive doped polyaniline comprised of an ionized polyaniline backbone polymer and one or more dopant solute species selected from the group consisting of:

wherein R.sub.1 is the same or different at each occurrence and is a substituted or unsubstituted organic radical, and r is a positive whole number equal to or greater then 1. Another aspect of this invention is articles formed from this polyaniline. This invention also relates to a composition comprising a matrix of one or more thermoplastic polymers having one or more doped polyanilines of this invention dispersed therein, and to articles formed from this composition. This invention also relates to a process for forming the compositions of this invention by melt-blending one or more doped polyaniline of this invention and one or more thermoplastic polymers.

As used herein, "polyanilines" are homopolymers or copolymers in which at least 50 mole % of the recurring monomeric units are derived from unsubstituted or substituted anilines of the formula: ##STR1## wherein: n is an integer from 0 to 4;

m is an integer from 1 to 5 with the proviso that the sum of n and m is equal to 5;

R.sub.2 and R.sub.4 are the same or different and are R.sub.3 substituents, hydrogen or alkyl with the proviso that at least one of R.sub.2 or R.sub.4 is hydrogen; and

R.sub.3 is the same or different at each occurrence and is selected from the group consisting of deuterium, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, aryloxyalkyl, alkylsulfinylalkyl, alkoxyalkyl, alkylsulfonyl, phosphonic acid, borate, carboxylate, phosphonate, sulfonate, phosphinate, arylthio, sulfinate, sulfinic acid, alkylsulfonylalkyl, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, hydroxy, cyano, sulfonic acid, nitro, or alkylsilane; or alkyl substituted with one or more sulfonic acid, phosphoric acid, phosphonic acid, sulfinate, sulfinic acid, borate, carboxylate, phosphonate, sulfonate, phosphinate, boric acid, carboxylic acid, halo, nitro, cyano or epoxy moieties; or any two R.sub.3 groups together or an R.sub.3 group together with any R.sub.4 or R.sub.2 group may form an alkylene or alkenylene chain completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur, sulfinyl, ester, carbonyl, sulfonyl, or oxygen atoms; or R.sub.3 is an aliphatic moiety having repeat units of the formula:

wherein q is a positive whole number; with the proviso that said homopolymer or copolymer includes about 10 or more recurring aniline moieties in the polymer backbone.

As used herein, an "organic radical" is polymeric or other type of radical.

BRIEF DESCRIPTION OF DRAWINGS

In the drawings,

FIG. 1 is a thermogravimetric analysis (TGA) spectrum under argon or poly(aniline chloride) as prepared in Example 1.

FIG. 2 is a thermogravimetric analysis (TGA) spectrum under argon of poly(aniline 1,5-naphthalene disulfonate) as prepared in Example 2.

FIG. 3 is a thermogravimetric analysis (TGA) spectrum under argon of poly(aniline p-toluene sulfonate) as prepared by redoping neutral polyaniline (Example 3).

FIG. 4 is a thermogravimetric analysis (TGA) spectrum under argon of poly(aniline p-toluene sulfonate) as prepared in Example 4.

FIG. 5 is a thermogravimetric analysis (TGA) spectrum under argon of poly(aniline dodecyl-benzene sulfonate) as prepared in Example 5.

FIG. 6 is a thermogravimetric analysis (TGA) spectrum under argon of poly(aniline 1,3-benzene disulfonate) as prepared in Example 6.

FIG. 7 is a thermogravimetric analysis (TGA) spectrum under argon of poly(aniline-sulfonate) as prepared in Example 7.

FIG. 8 is a graph showing percent weight loss as a function of temperature for polyaniline doped with chloride anions.

FIG. 9 is a graph showing percent weight loss as a function of temperature for polyaniline doped with tosylate anions.

DETAILED DESCRIPTION OF THE INVENTION

The thermally stable electrically conductive polyaniline of this invention comprises two essential ingredients. One essential ingredient is a substituted or unsubstituted polyaniline. In general, polyanilines for use in the invention are homopolymers and copolymers derived from the polymerization of unsubstituted and substituted anilines of the Formula I: ##STR2## wherein: n is an integer from 0 to 4;

m is an integer from 1 to 5 with the proviso that the sum of n and m is equal to 5;

R.sub.2 and R.sub.4 are the same or different and are R.sub.3 substituents, hydrogen or alkyl; and

R.sub.3 is the same or different at each occurrence and is selected from the group consisting of alkyl, deuterium, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, aryloxyalkyl, alkylsulfinylalkyl, alkoxyalkyl, phosphonic acid, alkylsulfonyl, arylthio, alkylsulfonylalkyl, boric acid, phosphoric acid, sulfinate, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, phosphonic acid, halogen, hydroxy, cyano, sulfinic acid, carboxylate, borate, phosphate, sulfonate, phosphinate, phosphonate, phosphonic acid, sulfonic acid, nitro, alkylsilane or alkyl substituted with one or more phosphonic acid, sulfonic acid, phosphoric acid, boric acid, carboxylate, borate, sulfonate, phosphinate, phosphonate, phosphate acid, phosphinic acid, carboxylic acid, halo, nitro, cyano or epoxy moieties; or any two R.sub.3 groups together or any R.sub.3 group together with any R.sub.1 or R.sub.2 group may form an alkylene or alkenylene chain completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur, sulfinyl, ester, carbonyl, sulfonyl, or oxygen atoms; or R.sub.3 is a divalent organic moiety bonded to the same or a different substituted or unsubstituted aniline moiety or R.sub.3 is an aliphatic moiety having repeat units of the formula:

wherein q is a positive whole number; with the proviso that said homopolymer and copolymer includes about 10 or more recurring substituted or unsubstituted aniline aromatic moieties in the polymer backbone.

Illustrative of the polyanilines useful in the practice of this invention are those of the Formulas II to V: ##STR3## wherein: z is an integer equal to or greater than 1.

x is an integer equal to or greater than about 1, with the proviso that the ratio of x to y is greater than or equal to about 0.5; and

z, v and u are the same or different and are integers equal or greater than 1.

The following listing of substituted and unsubstituted anilines are illustrative of those which can be used to prepare polymers and copolymers useful in the practice of this invention.

______________________________________ 2-Cyclohexylaniline 2-Acetylaniline Aniline 2,5-Dimethylaniline o-Toluidine 2,3-Dimethylaniline 4-Propanoylaniline N,N-Dimethylaniline 2-(Methylamino)aniline 4-Benzylaniline 2-(Dimethylamino)aniline 4-Aminoaniline 2-Methyl-4-methoxy- 2-Methylthiomethylaniline carbonylaniline 4-(2,4-Dimethylphenyl) 4-Carboxyaniline aniline N-Methyl aniline 2-Ethylthioaniline N-Propyl aniline N-Methyl 2,4-Dimethylaniline N-Hexyl aniline N-Propyl m-Toluidine m-Toluidine N-Methyl o-Cyanoaniline o-Ethylaniline 2,5-Dibutylaniline m-Ethylaniline 2,5-Dimethoxyaniline o-Ethoxyaniline Tetrahydronaphthylamine m-Butylaniline o-Cyanoaniline m-Hexylaniline 2-Thiomethylaniline m-Octylaniline 2,5-Dichloroaniline 4-Bromoaniline 3-(n-Butanesulfonic acid) 2-Bromoaniline aniline 3-Bromoaniline 3-Propoxymethylaniline 3-Acetamidoaniline 2,4-Dimethoxyaniline 4-Acetamidoaniline 4-Mercaptoaniline 5-Chloro-2-methoxy-aniline 4-Ethylthioaniline 5-Chloro-2-ethoxy-aniline 3-phenoxyaniline N-Hexyl-m-Toluidine 4-phenoxyaniline 4-phenylthioaniline N-Octyl m-Toluidene 3-amino-9-methylcarbazole 4-trimethylsilyaniline 4-amino carbazole 3-amino carbazole N-(p-amino phenyl) aniline ______________________________________

Exemplary of useful R.sub.2 and R.sub.4 groups are hydrogen, methyl, ethyl, isopropyl, butyl, isobutyl, hexyl, octyl and the like.

Illustrative of useful R.sub.3 groups are hydrogen, alkyl, such as methyl, ethyl, octyl, nonyl, tert-butyl, neopentyl, isopropyl, sec-butyl, dodecyl and the like, alkenyl such as 1 -propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl and the like; alkoxy such as propoxy, butoxy, methoxy, isopropoxy, pentoxy, nonoxy, ethyoxy, octoxy, and the like; cycloalkenyl such as cyclohexenyl, cyclopentenyl and the like; alkanoyl such as butanoyl, pentanoyl, octanoyl, ethanoyl, propanoyl and the like; alkylsulfinyl, alkylsulfonyl, alkylthio, arylsulfonyl, arylsulfonyl, and the like, such as butylthio, neopentylthio, methylsulfinyl, benzylsulfinyl, phenylsulfinyl, propylthio, octylthio, nonylsulfonyl, octylsulfonyl, methylthio, isopropylthio, phenylsulfonyl, methylsulfonyl, nonylthio, phenylthio, ethylthio, benzylthio, phenethylthio, sec-butylthio, naphthylthio and the like; alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like; cycloalkyl such as cyclohexyl, cyclopentyl, cyclooctyl, cycloheptyl and the like; alkoxyalkyl such as methoxy-methylene, ethoxymethyl, butoxymethyl, propoxyethyl, pentoxybutyl and the like; aryloxyalkyl and aryloxyaryl such as phenoxyphenyl, phenoxymethylene and the like; and various substituted alkyl and aryl groups such as 1-hydroxybutyl, 1-aminobutyl, 1-hydroxylpropyl, 1-hydroxypentyl, 1-hydroxyoctyl, 1-hydroxyethyl, 2-nitro-ethyl, trifluoromethyl, 3,4-epoxybutyl, cyanomethyl, 3-chloropropyl, 4-nitrophenyl, 3-cyanophenyl, and the like; alkyl or aryl groups terminated with phosphonic acid, phosphinic acid, sulfinate, sulfonic acid, sulfinic acid, phosphoric acid, boric acid, or carboxylic acid groups such as ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid, phenylsulfonic acid, and the corresponding phosphoric acid, boric acid, sulfonic acid, carboxylic acid, sulfinate, sulfinic acid, phosphonic acid, and phosphinic acid.

Also illustrative of useful R.sub.3 groups are divalent moieties derived from any two R.sub.3 groups or a R.sub.3 group with an R.sub.1 or R.sub.2 group such as moieties of the formula:

wherein a is an integer from about 3 to about 7, and b is an integer from 1 to 2 and R.sub.5 is the same or different at each occurrence and is hydrogen or alkyl, as for example --(CH.sub.2)--.sub.4, --(CH.sub.2)--.sub.3 --(CH.dbd.CH--CH.dbd.CH)--[--(H.sub.2 --CHCCH.sub.3)--CH.sub.2 --],[--(CCH.sub.3)H].sub.3 -- and --(CH.sub.2)--.sub.5, or such moieties which optionally include heteroatoms of oxygen, nitrogen, ester, sulfonyl, carbonyl, sulfinyl, and/or sulfur such as --CH.sub.2 SCH.sub.2 -- --CH.sub.2 NHCH.sub.2, --SCH.sub.2 NHCH.sub.2 --, --O--CH.sup.2- S--CH.sub.2 --, --CH.sub.2 S(O.sub.2)CH.sub.2 --, --CH.sub.2 S(O)CH.sub.2 --, --OC(O)CH.sub.2 CH.sub.2, --CH.sub.2 C(O)CH.sub.2 and --CH.sub.2 --O--CH.sub.2 -- to form heterocyclic amino compounds such as tetrahydronaphthylamine, dihydrobenzopyrroleamine, benzofuranamine, dihydrobenzopyranamine, dihydrobenzofuranamine, dihydrobenzoparoxazineamine, dihydrobenzoparadiazineamine, dihydrobenzotetrazoleamine, dihydrobenzothiazineamine, benzothiopyranamine, dihydrobenzoxazoleamine and the like. Exemplary of useful R.sub.3 groups are divalent alkenylene chains containing 1 to about 3 unsaturated bonds such as divalent 1,3-butadiene and like moieties which may also include one or more divalent oxygen, nitrogen, sulfinyl, sulfonyl, carbonyl, ester, and/or sulfur groups which form such compounds as benzodiazineamine, benzodiazoleamine, benzotriazepineamine, benzoimidazolylamine, benzoxazoleamine, benzoixazoleamine, benzoxazolylamine, benzotriazineamine, benzoxazineamine, naphthaleneamine, benzopyranamine, benzothiazineamine, anthraceneamine, aminobenzothiopyran, aminobenzodiazine, benzethiopyrone, aminocoumarin, benzothiophene, benzothiodiazoleamine, and the like.

Preferred for use in the practice of this invention are polyanilines of the above Formulas II to V in which:

n is an integer from 0 to about 2;

m is an integer from 3 to 5, with the proviso that the sum of n and m is equal to 5;

R.sub.2 and R.sub.4 are the same or different at each occurrence and are hydrogen, methyl or ethyl;

R.sub.3 is alkyl or alkoxy having from 1 to about 30 carbon atoms, cyano, halogen, or alkyl substituted with phosphonic acid, phosphate, phosphoric acid, borate, sulfonate, carboxylate, phosphonate, boric acid, phosphinic acid, phosphinate, carboxylic acid or sulfonic acid substituents;

x is an integer equal to or greater than 1;

y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about 1;

z is an integer equal to or greater than about 5;

u is an integer equal to or greater than about 3; and

v is an integer equal to or greater than about 10.

Particularly preferred for use in the practice of this invention are polyanilines of the above Formulas II to V in which:

n is an integer from 0 to 2;

m is an integer from 3 to 5, with the proviso that the sum of n and m is equal to 5;

R.sub.2 and R.sub.4 are the same or different at each occurrence and are hydrogen or methyl;

R.sub.3 is alkyl or alkoxy having from 1 to about 20 carbon atoms, or alkyl substituted with carboxylic acid, phosphonic acid, phosphate, phosphoric acid, borate, sulfonate, carboxylate, phosphonate, or sulfonic acid substituents;

x is an integer equal to or greater than 2;

y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about 2;

z is an integer equal to or greater than about 10;

u is an integer equal to or greater than about 5; and

v is an integer equal to or greater than about 20.

Amongst the particularly preferred embodiments, most preferred for use in the practice of this invention are polyanilines of the above Formulas III or V in which:

n is an integer from 0 to 1;

m is an integer from 4 to 5, with the proviso that the sum of n and m is equal to 5;

R.sub.2 and R.sub.4 are hydrogen;

R.sub.3 is alkyl or alkoxy from 1 to about 15 carbon atoms;

x is an integer equal to or greater than 2;

y is equal to or greater than 1, with the proviso that the ratio of x to y is greater than about 2; and

u is an integer equal to or greater than about 6. In the most preferred embodiments of this invention, the polyaniline is derived from unsubstituted or alkyl substituted aniline.

In general, the number of aniline repeat units is at least about 10. In the preferred embodiments of the invention, the number of aniline repeat units is at least about 20, and in the particularly preferred embodiments, the number of repeat units is at least about 30. Amongst the particularly preferred embodiments, most preferred are those embodiments in which the number of repeat units is at least about 40.

Any form of substituted and unsubstituted polyaniline can be conveniently used in the practice of this invention. Illustrative of useful forms are those described in Green, A. G. and Woodhead, A. E., "Aniline-black and Allied Compounds, Part I", J. Chem. Soc., vol. 101, pp. 1117 (1912) and Kobayashi, et al., "Electrochemical Reactions . . . of Polyaniline Film-Coated Electrodes", J. Electroanal. Chem., Vol 177, pp. 281-91 (1984), which is hereby incorporated by reference. For example, unsubstituted polyaniline, useful forms include leucoemeraldine, protoemeraldine, emeraldine, nigraniline and tolu-protoemeraldine forms.

Useful polyanilines can be prepared through use of chemical and electrochemical synthetic procedures. For example, one form of polyaniline can be prepared by treating aniline with ammonium persulfate (NH.sub.4).sub.2 S.sub.2 O.sub.8 in excess 1M HCl. This powdered form of polyaniline is blue green in color. After methanol washing and air drying this material exhibits a conductivity of 10 S/cm. This conductive form of polyaniline can be treated with ammonium hydroxide in ethanol to form a non-conductive form of polyaniline which is purple in color and which has a conductivity of less than 10.sup.-8 S/cm. Other chemical procedures for preparation of various chemical forms of polyaniline are described in detail in Green et al. described above.

Useful forms of polyaniline can also be prepared electrochemically. For example, useful forms of polyaniline can be prepared by the electrochemical oxidation of aniline in aqueous fluoroboric acid electrolyte on a platinum foil anode.

Other chemical and electrochemical syntheses and transformations of the conductive form of polyaniline may be discovered and are presently contemplated as being useful. Moreover, additional forms or types of polyaniline may be elucidated in the future. Accordingly, no limitation to the syntheses, transformation, or structures herein described or postulated is intended beyond the limitations of the appended claims.

The second essential ingredient of the thermally stable polyaniline of this invention is a dopant solute. The purpose of the dopant is to render polyaniline electrically conductive. In general, such dopant solute is derived from a compound, which upon addition to the polyaniline, ionizes the polymer with co-committent formation of a dopant solute species. Illustrative of useful dopant species are those formed from ionization of neutral ionic compounds, polymers or the like selected from the group consisting of:

and having one or more cationic moieties selected from the group consisting of:

M.sup.+n

wherein:

R.sub.1 is an organic radical, amino, alkylamino, dialkylamino, arylamino, diarylamino, or alkylarylamino;

M is a species having a positive charge equal to n; and

n and r are the same and are 1 to 8.

The R.sub.1 group may vary widely and can be a substituted or unsubstituted aliphatic radical such as alkyl, nitroalkyl, haloalkyl and the like, or a substituted or unsubstituted aromatic radical such as phenyl, halophenyl, nitrophenyl, anthracyl, naphthyl, phenanthryl and the like. R.sub.1 may also be a polymeric radical such as a polymer having recurring pendant phenyl groups in the polymeric backbone substituted with sulfonic acid, phosphoric acid, phosphonate, phosphonic acid, sulfinate, sulfinic acid, phosphate, carboxylate, sulfonate, borate, phosphinate, carboxylic acid, boric acid, or phosphonic acid moieties such as sulfonated or phosphonated polystyrene, poly(2-methylstyrene), poly(4-phenylstyrene), poly(.alpha.-vinyl naphthalene), poly(vinyl benzoate), poly(benzyl methacrylate) and the like. In the particularly preferred embodiments of the invention, R.sub.1 is an aromatic radical and in the most preferred embodiments R.sub.1 is substituted or unsubstituted phenyl or naphthyl.

The nature of the M.sup.+n group may vary widely. For example, M.sup.+n may be a non-metal cation such as Bu.sub.4 N.sup.+, H.sup.+, NO.sup.+, NO.sub.2 .sup.+ NH.sub.4 .sup.+ and the like, or may be a metal cation such as Na.sup.+, Li.sup.+, Ag.sup.+, Ba.sup.+2, Co.sup.+3, Al.sup.+3, Fe.sup.+3, and the like.

The following is a listing of dopants which are useful in the practice of this invention for formation of the dopant solute.

1-anthracene sulfonic acid,

9-anthracene sulfonic acid,

2-phenathrene sulfonic acid,

3-phenanthrene sulfonic acid,

9-phenanthrene sulfonic acid,

NO.sub.2 CF.sub.3 SO.sup.-.sub.3,

CF.sub.3 SO.sub.3 H,

perfluoro octyl sulfonic acid

perfluoro octyl carboxylic acid

octylsulfonic acid,

dodecylsulfonic acid,

cetylsulfonic acid,

toluenesulfonic Acid (TsOH),

Fe(OTs).sub.3,

Fe(CH.sub.3 SO.sub.3).sub.3,

(FSO.sub.3).sub.2,

AgOTs,

Me.sub.3 SiOTs,

dodecylbenzene sulfonic acid,

naphthalene sulfonic acid,

benzene disulfonic acid,

benzene sulfonic acid,

1,3-benzene disulfonic acid,

2,5-dihydroxy-1,4-benzene disulfonic acid,

camphor sulfinic acid

naphthalene trisulfonic acid

dodecylbenzene sulfonic acid,

isethionic acid,

1,5-naphthalene disulfonic acid,

nickel phthalocyanine tetrasulfonic acid,

phenyl phosphonic acid,

poly(vinyl sulfonic acid),

3-sulfopropyl acrylate,

3-sulfopropyl methacrylate,

sulfamic acid,

5-sulfosalicyclic acid,

tiron (4,5-dihydroxy-1,3-benzene disulfonic acid),

vinyl sulfonic acid,

sulfanilic acid,

4-sulfophthalic acid,

sulfoacetic acid,

methyl orange,

sulfonated polystyrene,

sulfonated poly (.alpha.-vinyl naphthalene),

naphthol yellow,

naphthol blue black,

1,2-naphthoquinone-4-sulfonic acid,

naphthylazoxine S,

1-octane sulfonic acid,

t-butyl phosphonic acid,

ethyl phosphonic acid,

butyl phosphonic acid,

1,2-benzene disulfonic acid,

4-octylbenzene sulfonic acid,

2-mesitylene sulfonic acid,

2,6-naphthalene disulfonic acid,

2-naphthalene sulfonic acid,

1,3,6-naphthalene trisulfonic acid,

1,3,7-naphthalene trisulfonic acid,

sulfonazo III acid,

biphenyl disulfonic acid,

biphenyl sulfonic acid,

1,8-dihydroxynaphthalene-3,6-disulfonic acid,

3,6-dihydroxynaphthalene-2,7-disulfonic acid,

4,5-dihydroxynaphthalene-2,7-disulfonic acid,

6,7-dihydroxy-2-naphthalene sulfonic acid,

1-naphthalene phosphoric acid,

1-naphthalene sulfonic acid,

1-naphthalene-5,7-dinitro-8-hydroxy,

1-naphthalene-4-hydroxy sulfonic acid,

4-bromo benzene sulfonic acid,

4-hydroxy-5-isopropyl-2-methyl benzene sulfonic acid

3,4-diamino benzene sulfonic acid

benzenphosphoric acid,

1,3,5-benzene trisulfonic acid,

2-methyl-5-isopropyl benzene sulfonic acid,

3,4-dinitro benzene sulfonic acid,

2-methoxy benzene sulfonic acid,

1-naphthalene-5-hydroxy sulfonic acid,

1-naphthalene-7-hydroxy sulfonic acid,

1-naphthalene-3-hydroxy sulfonic acid,

2-naphthalene-1-hydroxy sulfonic acid,

4-phenylamino benzene sulfonic acid, ##STR4## wherein: M is a metal or non-metal cation;

c is 1, 2, 3 or 4;

d is 0, 1 or 2;

f is 0, 1 or 2;

g is 0, 1 or 2;

e is 0, 1 or 2; and

R.sub.6 is nitro, cyano, hydroxy, halogen, alkoxy, phosphate, borate, carboxylate, substituted or unsubstituted aryl or alkyl having from 1 to about 30 carbon atoms wherein permissible substituents include perhaloalkyl, phenyl, alkoxy, halogen, cyano, haloalkyl, hydroxy, sulfonic acid, phosphoric acid, boric acid, sulfinate, sulfinic acid, carboxylic acid, nitro, carboxylate and the like, or any two R.sub.6 substituents together may form an alkenylene chain completing a fused-ring system which chain may be unsubstituted or substituted with one or more halogen, phosphoric acid, hydroxy, boric acid, nitro, cyano, sulfinate, phosphoric acid, sulfinic acid, phosphate, carboxylate, phosphonic acid, phosphonate, sulfonate, borate, sulfonic acid or carboxylic acid groups, or R.sub.6 is a moiety of the formula:

wherein:

q is a positive whole number from 1 to about 10; and

In the particularly preferred embodiment of this invention useful dopants are those of the above formula wherein:

c is 1, 2 or 3;

d is 0 or 1;

f is 0 or 1;

g is 0 or 1;

e is 0, 1 or 2; and

R.sub.6 is substituted or unsubstituted phenyl or alkyl