Title of Invention	"A PROCESS FOR THE PREPARATION OF NOVEL CONDUCTING POLYANILINE GEL "
Abstract	A process for the preparation of novel conducting polyaniline gel by polymerization of aromatic amines in the presence of in aqueous medium, in the presence of an oxidizing agent at temperature in the rnage of 0°C to 60°C, for a period ranging between 2 to 24 hours, collecting the resultant oproduct to obtain polyaniline gel.

Full Text

This invention relates to a process for the preparation of novel polyaniline gel in water in its conducting, form. More particularly it relates to a process for the preparation of polyaniline gel in aqueous medium in its conducting form, known as the emeraldine salt form. This compound has the general formula 1 in the drawing shown below wherein R = H or CH/j and Rx = alkyl sulphonate or its sodium salt with x=7- 12.(Figure Removed) Formula 1 The novel polyaniline gel prepared by the process of this invention could be used to process high quality conductive polyaniline film, just prior to gelation. Considerable attention has been focused on polyaniline in the recent years since this material possesses interesting electrical and optical properties, well suited to such a variety of applications. Protonation-deprotonation processes can reversibly control its electrical properties. It can exist in several molecular forms, differing in chemical compositions, structures and electrical conductivity. All these forms can be in! i.TCoiiverled into cadi oilier by chemical or electrochemical oxidation. Processing difficulties due to its inherent insolubility and infusibility considerably hampers the industrial development of conductive polyaniline prepared chemically by conventional methods. The development of synthetic methodology to get processable polyaniline is of great interest because of the advantages offered by the material in post-synthesis processing. There are three possible methods for improving the processibility of polyanilines: 1. Preparation of polyaniline dispersions, However, the Polyaniline dispersions reported so far precipitate rapidly, thus limiting the storage stability of the material. 2. Prefunctionalisation of the starting monomer with a suitable group prior to polymerisation. The products obtained were found to be intractable in the acid form and can be made soluble only by converting it into the non-conductive base form. 3. Formation of the polymer salt using an acid functionalised by a large non-polar substituent known as counterion induced processibility. The research so far carried out using this method introduced polyanilines soluble in organic solvents There are no reports of conductive processable polyaniline gel in water. The process for the preparation of novel polyaniline gel in its conducting form as described and claimed by this invention is reported for the first time. The main object of the present invention is to provide a process for the preparation of novel conductive polyaniline gel in water, to overcome the drawback of proccssability problem of polyaniline, in its conducting form, namely the emeraldine salt. Another object is to provide a process for the preparation of conductive polyaniline gel in water using alkyl and alkyl aryl sulphonic acids as the protonating agent, which have surfactant properties. Yet another object of the invention is to provide a process wherein the synthesised processable emeraldine salt is a gel in water. Still another object of the present invention is to provide a process for the preparation of conductive polynailine gel in water from which high quality, thick and thin conductive polyaniline films could be processed just prior to gelation. • Accordingly, the present invention provides a process for the preparation of conductive processable novel polyaniline gel in water in its conducting form, of formula 1 in the drawing accompanying wherein R = H or CHs and Rx = alkyl sulphonate or its sodium salt with x =7 - 12, which comprises polymerising aromatic amine in the presence of a sulphonic acid, in aqueous medium, in the presence of an oxidising agent at a temperature in the range of 0°C to 60°C, for a period ranging between 2 to 24 hours, collecting the resultant product to obtain polyaniline gel of formula 1. (Figure Removed) Formula 1 In an embodiment of the present invention, the aromatic amines used for polymerisation may be aniline or substituted aromatic amines selected from o-toluidine, m-toluidine. In another embodiment, the sulphonic acid used may be selected from alkyl sulphonic acid, octane sulphonic acid, nonane sulphonic acid, decane sulphonic acid, dodecane sulphonic, or alkyl aryl sulphonic acid such as dodecyl benzene sulphonic acid.In still another embodiment of the invention, the oxidising agent used may be selected from ammonium persulphate, potassium persulphate, potassium bromate, potassium iodate, sodium iodate, potassium dichromate, potassium permanganate. The amount of oxidising agent used may be in ihc range of 0.5 to 3 %. The process of the present invention is described with reference to the following examples, which are illustrative only and should not be construed to limit the scope of this invention, in any manner. Example 1 0.816 gram of 1-dodecane sulphonic acid sodium salt was dissolved in 25 mL of dcionised water. To this 3 mL of 1 molar hydrochloric acid was added. To the above solution, 0.08 mL of aniline was added slowly and mixed thoroughly. 0.272 gram of ammonium persulphate was added to this mixture. The reaction was allowed • to proceed at 25°C for 12 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nSC>3~ Na, n = 11, R = H. The yield obtained was 29 grams. Example 2 1.75 grams of sodium dodecyl benzene sulphonate were dissolved in 100 mL of deionised water. To this 5 mL of 1 molar hydrochloric acid was added. To the above solution, 0.43 gram of m-toludine was added slowly and mixed thoroughly. 0.96 gram of potassium permanganate was added to this mixture. The reaction was allowed to proceed at 20°C for 14 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03" , n = 12, R = CH3. The yield obtained was 107 grams. Examples 0.549 gram of 1-decane sulphonic acid sodium salt was dissolved in 50 mL of deionised water. To this 1.5 mL of 1 molar hydrochloric acid was added. To the above solution, 0.114 mL of aniline was added slowly and mixed thoroughly. 0.40 gram of potassium iodate was added to this mixture. The reaction was allowed to proceed at 17°C for 12 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03' Na, n = 10, R = H. The yield obtained was 53 grams. Example 4 0.69 gram of 1-nonane sulphonic acid, sodium salt was dissolved in 75 mL of deionised water. To this 3 mL of 1 molar hydrochloric acid was added. To the above solution, 0.28 gram of o-toluidine was added slowly and mixed thoroughly. 1.2 gram of potassium dichromate was added to this mixture. The reaction was allowed to proceed at 25°C for 24 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = Cl-^CI^nSCV Na+, n = 9, R = CH3. The yield obtained was 79 grams. Example 5 0.70 gram of sodium dodecyl benzene sulphonate was dissolved in 50 mL of deionised water. To this 2 mL of 1 molar hydrochloric acid was added. To the above solution, 0.16 mL of aniline was added slowly and mixed thoroughly. 0.60 gram of potassium persulphate was added to this mixture. The reaction was allowed to proceed at 45°C for 4 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CI-^CHbXiSCh" , n = 12, R = H. The yield obtained was 52 grams. Kxamplc 6 0.88 gram of sodium dodecyl benzene sulphonatc was dissolved in 100 mL of deionised water. To this 2.5 mL of 1 molar hydrochloric acid was added. To the above solution, 0.18 mL of aniline was added slowly and mixed thoroughly. 0.69 gram of ammonium persulphate was added to this mixture. The reaction was allowed to proceed at 15°C for 6 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CHsCCFbJnSCV , n = 12, R = H. The yield obtained was 102 grams. • Example 7 1.2 grams of 1-dodecane sulphonic acid, sodium salt were dissolved in 75 mL of deionised water. To this 3.4 mL of 1 molar hydrochloric acid was added. To the above solution, 0.273 gram of m-toluidine was added slowly and mixed thoroughly. 1.3 grams potassium iodate was added to this mixture. The reaction was allowed to proceed at 55°C for 6 hours. The product obtained was polyaniline gel in-its conducting form of formula 1 wherein Rx = CrtyCI-^nSCb" Na, n = 11, R = CH/j. The yield obtained was 78 grams. Example 8 0.87 gram of sodium dodecyl benzene sulphonate was dissolved in 100 mL of deionised water. To mis 2.5 mL of 1 molar hydrochloric acid was added. To the above solution, 0.22gram of m-toluidine was added slowly and mixed thoroughly. 0.63 gram of potassium permanganate was added to this mixture. The reaction was allowed to proceed at 20°C for 10 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03', n = 12, R = CH3. The yield obtained was 104 grams. Example 9 0.16 gram of 1-octane sulphonic acid, sodium salt was dissolved in 25 mL of deionised water. To this 0.75 mL of 1 molar hydrochloric acid was added. To the above solution, 0.067 gram of 0-toluidinc was added slowly and mixed thoroughly. v- 0.22 grain of ammonium persulphate was added to this mixture. The reaction was allowed to proceed at 25°C for 12 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03" Na"1", n = 8, R = Clij. The yield obtained was 27.5 grams. Example 10 3.49 grams of sodium dodecyl benzene sulphonate were dissolved in 200 mL of deionised water. To this 10 mL of 1 molar hydrochloric acid was added. To the above solution, 0.75 gram of m-toluidine was added slowly and mixed thoroughly. 3.6 grams of potassium persulphate were added to this mixture. The reaction was allowed to proceed at 18°C for 15 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CHaCCH^nSOs" Na+, n = 12, R = CHs. The yield obtained was 222 grams. • Example 11 1.5 grams of 1-decane sulphonic acid sodium salt were dissolved in 150 mL of deionised water. To this 6 mL of 1 molar hydrochloric acid was added. To the above solution, 0.52 gram of 0-toluidine was added slowly and mixed thoroughly. 1.6 grams of ammonium persulphate were added to this mixture. The reaction was allowed to proceed at 20°C for 12 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = ClhCCI-^nSCV Na+, n = 10, R = CH3. The yield obtained was 159 grams. Example 12 0.78 gram of 1-dodecane sulphonic acid sodium stilt was dissolved in 75 mL of deionised water. To this 2.9 mL of 1 molar hydrochloric acid was added. To the above solution, 0.24 gram of m-toluidine was added slowly and mixed thoroughly. 0.96 gram of potassium iodate was added to this mixture. The reaction was allowed to proceed at 15°C for 20 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03" Na+, n = 11, R = CH3. The yield obtained was 80 grams. Example 13 • 1.46 grams of sodium dodecyl benzene sulphonate were dissolved in 200 mL of deionised water. To this 4.2 mL of 1 molar hydrochloric acid was added. To the above solution, 0.34 mL of aniline was added slowly and mixed thoroughly. 1.38 grams of potassium persulphate were added to this mixture. The reaction was allowed to proceed at 20°C for 8 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03' Na+, n = 12, R = H. The yield obtained was 202.5 grams. Example 14 1.0 gram of sodium dodecyl benzene sulphonate was dissolved in 100 mL of deionised water. To this 2.9 mL of 1 molar hydrochloric acid was added. To the above solution, 0.20 gram of o-toluidine was added slowly and mixed thoroughly. 0.40 gram of potassium iodate was added to this mixture. The reaction was allowed to proceed at 20°C for 16 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03' Na+, n = 12, R = CH3. The yield obtained was 79 grams. ExamplclS 1.3 grams of 1-nonane sulphonic acid, sodium salt were dissolved in 100 mL of deionised water. To this 5.5 mL of 1 molar hydrochloric acid was added. To the auove solution, 0.43 mL of aniline was added slowly and mixed thoroughly. 1.38 grams of potassium persulphate were added to this mixture. The reaction was allowed to proceed at 25°C for 12 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03", n = 9, R = H. The yield obtained was 102.5 grams. Example 16 3.76 grams of sodium dodecyl benzene sulphonate were dissolved in 250 mL of deionised water. To this 9.8 mL of 1 molar hydrochloric acid was added. To the above solution, 0.84 mL of aniline was added slowly and mixed thoroughly. 1.58 grams of ammonium persulphate were added to this mixture. The reaction was allowed to proceed at 17°C for 9 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = CH3(CH2)nS03~, n = 12, R = H. The yield obtained was 265 grams. Example 17 1.88 grams of sodium dodecyl benzene sulphonate were dissolved in 200 mL of deionisecl water. To this 5.4 mL of 1 molar hydrochloric acid was added. To the above solution, 0,42 ml. of nniline was added slowly and mixed thoroughly. 0.73 gram of potassium permanganate was added to this mixture. The reaction was allowed to proceed at 60°C for 4 hours. The product obtained was polyaniline gel in its conducting form of formula 1 wherein Rx = ClbtCII^nSCV , n = 12, R = H. The yield obtained was 207.5 grams. The advantages offered by the process of the invention are : 1. The products obtained as per the process of this invention are in a ready to use • conductive gel form. 2. The polyaniline gel prepared by the process of this invention can be easily processed to films prior to gelation. 3. The dedoping and redoping processes can be done effectively on the films processed. 4. The process is eco-friendly since water is used as the medium of reaction. We claim : 1. A process for the preparation of novel polyaniline gel in its conducting form, which comprises polymerisation of aromatic amines in the presence of an acid, in aqueous medium, in the presence of an oxidising agent at a temperature in the range of 0°C to 60°C, for a period ranging between 2 to 24 hours, collecting the resultant product to obtain polyaniline gel of formula 1 in the drawing accompanying wherein R = H or Cl-h and Rx = alkyl sulphonate or sulphate group with x =7 - 12..(Figure Removed) Formula 1 2. A process as claimed in claim I wherein the aromatic amine used for polymerisation is unsubstituted aniline or substituted anilines selected from o-toluidinc, m-toluidine. 3. A process as claimed in claim 1 and 2, wherein the sulphonic acid used is selected from alkyl sulphonic acid such as octane sulphonic acid, nonane sulphonic acid, decane sulphonic acid, dodecane sulphonic etc., or alkyl aryl sulphonic acid such as dodecyl benzene sulphonic acid. 4. A process as claimed in claim 1 to 3, wherein the oxidising agent used is selected from hydrogen peroxide, ammonium persulphate, potassium persulphate, potassium bromate, potassium iodate, sodium iodate, potassium dichromate, potassium permanganate, ammonium dichromate. 5. A process for the preparation of conductive processable novel polyaniline gel in water substantially as described herein with reference to the examples.

Documents:

40-del-2001-abstract.pdf

40-del-2001-claims.pdf

40-del-2001-correspondence-others.pdf

40-del-2001-correspondence-po.pdf

40-del-2001-description (complete).pdf

40-del-2001-form-1.pdf

40-del-2001-form-19.pdf

40-del-2001-form-2.pdf