Electrically conducting polyaniline: method for emulsion polymerization

Abstract

A method of emulsion polymerization of aniline or substituted anilines for making substituted or unsubstituted homopolymers and co-polymers of aniline. The method includes formation of an emulsion of aniline monomers, polar solvent, non-polar or weakly polar solvent and functionalized protonic acid, which is selected for its ability to perform two functions: acting as a surfactant and acting as a protonating agent (dopant) in producing an electrically conducting polymer. Then, an oxidant is added to polymerize the ingredients of the emulsion. This method provides polyaniline particles of highly crystalline and oriented morphologies of controlled aspect ratios.

We claim:  
     
       1. A method of forming an electrically conductive microfibrillar polyaniline which comprises the steps of: 
       a. forming an emulsion comprising  
       (i) a polar liquid,  
       (ii) a non-polar or weakly polar liquid that is immiscible with said polar liquid,  
       (iii) at least one aniline, and  
       (iv) at least one functionalized protonic acid which protonates and forms a complex with the aniline and which functionalized protonic acid emulsifies the polar liquid and the non-polar or weakly polar liquid; and  
       b. adding an oxidant to said emulsion to cause said aniline to polymerize.  
     
     
       2. The method of claim  1  wherein the polar liquid is water. 
     
     
       3. The method of claim  1  wherein the aniline is substituted aniline, unsubstituted aniline or a mixture thereof. 
     
     
       4. The method of claim  3  wherein the aniline has the following formula:                    
       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; and  
       R is independently selected so as to be the same or different at each occurrence and is selected from the group consisting of alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, cyano, or alkyl substituted with one or more sulfonic aid, carboxylic acid, halo, nitro, cyano or expoly moleties; or carboxylic acid, halogen, nitro, cyano, or sulfonic acid moieties; or any two R groups together 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 or oxygen atoms.  
     
     
       5. The method of claim  4  wherein n is 0 and m is 5. 
     
     
       6. The method of claim  1  wherein said electrically conductive polyaniline has one of the following structures:                    
       wherein: 
       n is an integer from 0 to 4;  
       m is an integer from 1 to 4 and the sum of n plus m equals 4;  
       R is independently selected so as to be the same or different at each occurrence and is selected from the group consisting of alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, cyano, or alkyl substituted with one or more sulfonic aid, carboxylic acid, halo, nitro, cyano or expoly moleties; or carboxylic acid, halogen, nitro, cyano, or sulfonic acid moieties; or any two R groups together 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 or oxygen atoms;  
       x is an integer equal to or greater than 1;  
       y is an integer equal to or greater than 0, with the proviso that the sum of x and y is greater than 1; and  
       z is an integer equal to or greater than 1.  
     
     
       7. The method of claim  6  wherein n is an integer from 0 to about 2; 
       m is an integer from 2 to 4, with the proviso that the sum of n and m is equal to 4;  
       R is alkyl or alkoxy having from 1 to about 12 carbon atoms, cyano, halogen, or alkyl substituted with carboxylic acid or sulfonic acid substituents;  
       x is an integer equal to or greater than 1;  
       y is an integer equal to or greater than 0, with the proviso that the sum of x and y is greater than about 4, and  
       z is an integer equal to or greater than about 5.  
     
     
       8. The method of claim  7  wherein 
       the sum of n and m is equal to 4;  
       R is alkyl or alkoxy having from 1 to about 4 carbon atoms or alkyl substituted with carboxylic acid or sulfonic acid substituents;  
       the sum of x and y is greater than about 6; and  
       z is an integer equal to or greater than about 10.  
     
     
       9. The method of claim  6  in which: 
       n is 0 or 1;  
       m is 3 or 4, with the proviso that the sum of n and m equals 4;  
       R is alkyl or alkoxy from 1 to about 4 carbon atoms;  
       x is an integer equal to or greater than 2;  
       y is an integer equal to or greater than 1, with the proviso that the sum of x and y is greater than about 8; and  
       z is an integer equal to or greater than about 15.  
     
     
       10. The method of claim  6  wherein n is 0 and m is 4. 
     
     
       11. The method of claim  1  wherein the emulsion of (a) further comprises one or more emulsifiers. 
     
     
       12. The method of claim  1  further comprising, after permitting the aniline to polymerize, the step of removing said polar and/or non-polar or weakly polar liquids. 
     
     
       13. The method of claim  1  wherein the functionalized protonic acid performs the dual functions of emulsifying the polar and non-polar liquids and of protonating/complexing with polyaniline. 
     
     
       14. The method of claim  1  wherein the electrically conductive polyaniline has a microfibrillar morphology such that the aspect ratio of the microfibrils is at least about 5. 
     
     
       15. The method of claim  1  wherein the electrically conductive polyaniline has a microfibrillar morphology such that the aspect ratio of the microfibrils is at least about 10. 
     
     
       16. The method of claim  1  wherein the electrically conductive polyaniline has a microfibrillar morphology such that the aspect ratio of the microfibrils is at least about 50. 
     
     
       17. The method of claim  1  wherein the electrically conductive polyaniline has a microfibrillar morphology such that the aspect ratio of the microfibrils is at least about 100. 
     
     
       18. A method of producing electrically conducting microfibrillar polymers of aniline, said method comprising 
       a. forming an emulsion comprising  
       (i) at least one non-polar or weakly polar organic liquid comprising 1-99% by weight of the emulsion;  
       (ii) a polar liquid that is not miscible with said non-polar or weakly polar liquid and that constitutes 1-99% by weight of the emulsion;  
       (iii) at least one aniline selected from unsubstituted anilines, substituted anilines and mixtures thereof;  
       (iv) at least one protonic acid solute, in which the counter-ion has been selected for its ability to simultaneously or independently:  
       (A) emulsify said emulsion; and  
       (B) form an electrically conducting complex with the polyaniline, said complex having an electrical conductivity of at least 10 −5  S/cm; and  
       v. one or more additional emulsifiers, and  
       b. contacting said emulsion with an oxidant.  
     
     
       19. The method of claim  18  wherein the aniline polymer is a homopolymer or co-polymer. 
     
     
       20. The method of claim  18  wherein the electrically conducting complex has a conductivity of at least 10 −3  S/cm. 
     
     
       21. The method of claim  18  wherein the electrically conducting complex has a conductivity of at least 10 =31 1  S/cm. 
     
     
       22. The method of claim  18  wherein the electrically conducting complex has an inherent viscosity of at least 1.2 dl/g. 
     
     
       23. The method of claim  18  wherein the electrically conducting complex has an inherent viscosity of at least 2.0 dl/g. 
     
     
       24. The method of producing electrically conducting microfibrillar polymers of aniline according to claim  18 , said method comprising 
       
         a. forming an emulsion comprising  
       
       ( i )  at least one non - polar or weakly polar organic liquid comprising  1 - 99   %  by weight of the emulsion, wherein the non - polar or weakly polar liquid comprising an aliphatic alcohol;    
       ( ii )  a polar liquid that is not miscible with said non - polar or weakly polar liquid and that constitutes  1 - 99   %  by weight of the emulsion, wherein said polar liquid is water;    
       ( iii )  at least one aniline selected from unsubstituted anilines, substituted anilines and mixtures thereof, wherein the aniline has the following formula:                      
         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 ; and  
       
         R is independently selected so as to be the same or different at each occurrence and is selected from the group consisting of alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, cyano, or alkyl substituted with one or more sulfonic acid, carboxylic acid, halo, nitro, cyano, or epoxy moieties; or carboxylic acid, halogen, nitro, cyano, or sulfonic acid moieties; or any two R groups together 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 or oxygen atoms;    
       ( iv )  at least one protonic acid solute, in which the counter - ion has been selected for its ability to simultaneously or independently;    
       ( A )  emulsify said emulsion; and    
       ( B )  form an electrically conducting complex with the polyaniline said complex having an electrical conductivity of at least  10 −5  S/cm; and  
       ( v )  one or more additional emulsifiers, and    
       
         b. contacting said emulsion with an oxidant. 
       
     
     
       25. The method of claim  18  wherein the non- polar or weakly polar liquid has a dielectric constant less than about  22 .   
     
     
       26. The method of claim  25  wherein the non- polar or weakly polar liquid is selected from the group consisting of alkanes and alkenes having from  5  to about  12  carbon atoms, mineral oil, aromatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated alkanes, aliphatic alcohols, alkyl ethers and ketones having from  4  to about  12  carbon atoms, cycloalkanes, cycloalkenes, carbon tetrachloride, carbon disulfide, chloroform, bromoform, dichloromethane, morpholine, alkylbenzenes, xylenes, toluene, decahydronaphthalene, styrene, and naphthalene.   
     
     
       27. The method of claim  25  wherein the polar liquid is water. 
     
     
       28. The method of claim  25  wherein the non- polar or weakly polar liquid comprises an aliphatic alcohol.   
     
     
       29. The method of claim  25  wherein the non- polar or weakly polar liquid is an alkyl ether having from  4  to about  12  carbon atoms.   
     
     
       30. The method of claim  25  wherein the non- polar or weakly polar liquid is a ketone having from  4  to about  12  carbon atoms.   
     
     
       31. The method of claim  1  wherein the non- polar or weakly polar liquid has a dielectric constant less than about  22 .   
     
     
       32. The method of claim  31  wherein the non- polar or weakly polar liquid is selected from the group consisting of alkanes and alkenes having from  5  to about  12  carbon atoms, mineral oil, aromatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated alkanes, aliphatic alcohols, alkyl ethers and ketones having from  4  to about  12  carbon atoms, cycloalkanes, cycloalkenes, carbon tetrachloride, carbon disulfide, chloroform, bromoform, dichloromethane, morpholine, alkylbenzenes, xylenes, toluene, decahydronaphthalene, styrene, and naphthalene.   
     
     
       33. The method of claim  32  wherein the non- polar or weakly polar liquid is an aliphatic alcohol.   
     
     
       34. The method of claim  32  wherein the non- polar or weakly polar liquid is an alkyl ether having from  4  to about  12  carbon atoms.   
     
     
       35. The method of claim  32  wherein the non- polar or weakly polar liquid is a ketone having from  4  to about  12  carbon atoms.   
     
     
       36. The method of forming an electrically conductive microfibrillar polyaniline according to claim  1 , which method comprises the steps of: 
       
         a. forming an emulsion comprising  
       
       ( i )  a polar liquid, wherein the polar liquid is water;    
       ( ii )  a non - polar or weakly polar liquid that is immiscible with said polar liquid, wherein the non - polar or weakly polar liquid has a dielectric constant less than about  22 ;    
       ( iii )  at least one aniline, wherein the aniline has the following formula:                      
         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 ; and  
       
         R is independently selected so as to be the same or different at each occurrence and is selected from the group consisting of alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, cyano, or alkyl substituted with one or more sulfonic acid, carboxylic acid, halo, nitro, cyano, or epoxy moieties; or carboxylic acid, halogen, nitro, cyano, or sulfonic acid moieties; or any two R groups together 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 or oxygen atoms; and    
       ( iv )  at least one functionalized protonic acid which protonates and forms a complex with the aniline and which functionalized protonic acid emulsifies the polar liquid and the non - polar or weakly polar liquid; and    
       
         b. adding an oxidant to said emulsion to cause said aniline to polymerize. 
       
     
     
       37. The method of forming an electrically conductive microfibrillar polyaniline according to claim  1 , wherein the polar liquid is water, the nonpolar or weakly polar liquid comprises an aliphatic alcohol and the at least one aniline is a single aniline such that the method comprise the steps of: 
       
         a. forming an emulsion comprising  
       
       ( i )  water;    
       ( ii )  an aliphatic alcohol;    
       ( iii )  an aniline; and    
       ( iv )  at least one functionalized protonic acid which protonates and forms a complex with the aniline and which functionalized protonic acid emulsifies the water and the aliphatic alcohol; and    
       
         b. adding an oxidant to said emulsion to cause said aniline to polymerize.