US5324453A
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Electrically conducting polyaniline: method for emulsion polymerization
Assignee: Neste Oyj
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Filing: 1992-08-07
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Granted: 1994-06-28
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Expires: 2012-08-07
Abstract
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.
Inventors
- 👤 Yong Cao
- 👤 Jan-Erik Osterholm
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 03:01
CPC Classifications
H; H01; H01B; H01B1/00; H01B1/06; H01B1/12; H01B1/124; H01B1/128; C; C08; C08G; C08G73/00; C08G73/02; C08G73/026; C08G73/0266
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
89 words
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.
Claim 2
Independent Claim
89 words
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.
Claim 3
Dependent Claim
11 words
The method of claim 1 wherein the polar liquid is water.
Claim 4
Dependent Claim
17 words
The method of claim 1 wherein the aniline is substituted aniline, unsubstituted aniline or a mixture thereof.
Claim 5
Dependent Claim
160 words
The method of claim 3 wherein the aniline has the following formula: ##STR3## 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.
Claim 6
Dependent Claim
13 words
The method of claim 4 wherein n is 0 and m is 5.
Claim 7
Dependent Claim
203 words
The method of claim 1 wherein said electrically conductive polyaniline has one of the following structures: ##STR4## 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.
Claim 8
Dependent Claim
109 words
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.
Claim 9
Dependent Claim
62 words
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.
Claim 10
Dependent Claim
88 words
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 alkoxyl 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.
Claim 11
Dependent Claim
13 words
The method of claim 6 wherein n is 0 and m is 4.
Claim 12
Dependent Claim
16 words
The method of claim 1 wherein the emulsion of (a) further comprises one or more emulsifiers.
Claim 13
Dependent Claim
25 words
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.
Claim 14
Dependent Claim
25 words
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.
Claim 15
Dependent Claim
27 words
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.
Claim 16
Dependent Claim
27 words
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.
Claim 17
Dependent Claim
27 words
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.
Claim 18
Dependent Claim
27 words
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.
Claim 19
Independent Claim
135 words
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.
Claim 20
Independent Claim
135 words
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.
Claim 21
Dependent Claim
14 words
The method of claim 18 wherein the aniline polymer is a homopolymer or co-polymer.
Claim 22
Dependent Claim
19 words
The method of claim 18 wherein the electrically conducting complex has a conductivity of at least 10 -3 S/cm.
Claim 23
Dependent Claim
19 words
The method of claim 18 wherein the electrically conducting complex has a conductivity of at least 10 -1 S/cm.
Claim 24
Dependent Claim
19 words
The method of claim 18 wherein the electrically conducting complex has an inherent viscosity of at least 1.2 dl/g.
Claim 25
Dependent Claim
19 words
The method of claim 18 wherein the electrically conducting complex has an inherent viscosity of at least 2.0 dl/g.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1997-06-27 | 1997-12-27 | 1998-06-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2001-06-27 | 2001-12-27 | 2002-06-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2005-06-27 | 2005-12-27 | 2006-06-28 | $7700.00 | Window Closed / Lapsed |