Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
  • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
  • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
  • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
  • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
  • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
  • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment
  • C08G65/485—Polyphenylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/026—Wholly aromatic polyamines
  • C08G73/0266—Polyanilines or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/04—Polysulfides

Definitions

• the present invention relates to inherently conductive polymers and their uses. More particularly, it relates to novel aqueous solutions of inherently conductive polymers and to methods for the preparation thereof. The present invention also concerns the use of the aqueous solutions for forming films and coating layers.
• Electronic components are easily damaged in the case of rapid discharging of the electrostatic current (electrostatic discharge, ESD), causing insulating areas and other defects in the conductive patterns. Therefore, electronic components and devices are often packed in electrically conductive packages that have optimally surface resistance in the range of 10 6 -10 9 ohm. Due to the large conductive surface of the package, possible electric charges are discharged in a controlled manner, without damaging the components.
• ESD electrostatic discharge
• plastic that can be in various forms such as rigid film or flexible foil.
• a typical way to make such packaging materials electrically conductive is by mixing carbon black or other conductive fillers into the polymer matrix.
• conductive fillers may migrate to the surface of the package and cause contamination of the product.
• fillers do not allow the control of the conductivity, but lead easily to highly conductive materials that are not optimal for ESD protection. Furthermore, most fillers lead to non-transparent materials.
• Another option would be conductors based on ionic conductivity, which is well known technology for antistatic applications. However, in this case the conductivity often requires conditions with high relative humidity of the air and the conductivity is often lost by time. Also, the level of conductivity is restricted in the lower end of the ESD protection, maximum surface resistance being typically 10 8 - 10 9 ohm.
• Paper and cardboard are often used as packing material for electronic components and devices. Paper as such has surface resistance of 10 9 -10 10 ohm. However, this resistance is achieved only at high air humidity.
• ICPs inherently conductive polymers
• the ICPs are polymers which typically are “doped” (furnished, processed) in order to generate charge carriers (holes and electrons).
• charge carriers holes and electrons.
• Common to all electrically conductive polymers are the conjugated double bonds of the backbone chain (alternate single and double bonds, delocalized ⁇ electron system), which enable the movement of the charge carriers.
• Electrically conductive polymers have both ionic and electronic conductivity. The conductivity of electrically conductive polymers can be regulated within the whole conductivity range, from an insulating material to a metallic conductor.
• the ICPs are generally poorly soluble in solvents and it is therefore difficult to formulate them for solvent application.
• a solution of an inherently conductive polymer in a polar solvent is provided.
• the inherently conductive polymer is present in the form of a complex formed by a polymer chain with conjugated double bonds and a polymeric, sulphonated doping agent generally comprising a rigid or semi-rigid backbone.
• the doping agent has a backbone containing aromatic repeating units.
• any inherently conductive polymer can be used provided that it can be reversibly doped.
• doped stands for a capability of the polymer to be complexed, oxidised or protonised or charged into conductive form.
• the polymers have a polymer chain with conjugated double bonds.
• inherently conductive polymers are insoluble in solvents, in particular in organic solvent and in solvents having a solubility parameter of ⁇ 11 (cal/cm 3 ) 172 .
• compositions can be produced by forming
• the monomers are in situ polymerized in the presence of the sulphonated polymer.
• novel compositions have a number of interesting and important uses including antistatic coatings for electronics packages and conductive patterns in printed electronics applications.
• compositions are characterized by what is stated in the characterizing part of claim 1.
• novel method according to the invention is characterized by what is stated in the characterizing part of claim 10 and the uses by what is stated in claims 19 to 22.
• packaging materials can easily be treated and coated by applying a conductive polymer in liquid (solution) form on the surface thereof.
• various conductive thin films can be formed from the solution phase by evaporating the solvent of the composition.
• Inherently conductive polymers can be incorporated into water-borne paint compositions comprising, e.g. an acrylic binder. Toxic solvents and high VOC solvents can be avoided.
• the process according to the present invention is uncomplicated and economical.
• dispersions of polyaniline are manufactured by a multi-step process, where aniline is first polymerized, then polyaniline particles are isolated from the reaction medium and the particles are re-dispersed in the selected solvent. This is not an optimal way to produce homogenous and stable polymer dispersions.
• the clear advantage of the present invention is that polymerization takes place in-situ in the presence of the soluble doping acid, which leads to highly homogenous, nanoscale dispersion of polyaniline in the selected solvent.
• the present invention provides a novel composition
• a solution of an inherently conductive polymer in a polar solvent The polymer is doped with a sulphonated polymer containing aromatic repeating units which form a rigid or semi-rigid backbone. Further, there is a sufficient amount of free sulphonic acid groups present on the sulphonated polymer residue for maintaining the complex in solution, i.e. in solvent phase.
• the doped, conductive complex of the sulphonated polymer is formed with a polymer comprising a conjugated polymeric chain.
• a polymer comprising a conjugated polymeric chain all polymers are suitable that are convertible via a reversible oxidation or reduction and/or via reversible protonisation or other deriving reactions (which can, to some extent, be described as a complexing or compensation reaction) into conjugated, positive or negative polymer chains, the charging of which is compensated by ions of the opposite charge.
• the polymer can exist in states of different conductivity, which normally have a different chemical composition. Polymers having a conductivity which can reach more than 10 ⁇ 2 S/cm are preferred.
• useful polymers include polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothianaphthene (PITN), polyheteroarylenvinylene (PArV), in which the heteroarylene group can be, e.g. thiophene or pyrrole, poly-p-phenylene (PpP), polyphenylensulphide (PPS), polyperinaphthaline (PPN), polyphthalocyanine (PPhc) and other conjugated polymers, their derivatives (i.e. polymers of derivatives e.g. substituted with side-chains on the ring or on the heteroatom [these derivatives being] of the monomers forming the above mentioned polymers) and their copolymers and their physical mixtures with each other.
• PAc polydiacetylene
• PAc polyacetylene
• PPy polypyrrole
• PAni poly
• the conjugated polymeric chain is selected from the group of polyaniline, polypyrrole and substituted poly(thiophene)s.
• the inherently conductive polymer is a doped complex of polyaniline, based on aniline or aniline derivatives as monomers, or poly(ethylenedioxythiophene). Polyaniline is particularly preferred.
• the polar solvent is, in particular, water or an alkanol (aliphatic alcohol) or mixtures thereof, such as aqueous solutions of alkanols.
• suitable aliphatic alcohols are methanol, ethanol, n- and isopropanol, n-, i- and t-butanol, amyl alcohol and n-hexanol.
• Many of the alkanols can be employed in the form of aqueous solutions having a concentration of alkanol of about 0.1 to 99.5 %, in particular about 0.5 to 98 % by volume of the total solution. Examples include aqueous solutions of C 1- ⁇ alkanols, e.g. one or several of the above mentioned lower alkanols, having a concentration of about 5 to 99 % by volume with respect to the alkanol.
• compositions can be characterized as true solutions in the respect that they are optically clear and translucent.
• the conductive complexes are present in the form of dispersed minute particles.
• the present aqueous or alkanolic solutions comprise particles of doped polyaniline having a hydrodynamic radius of 10 to 300 nm, in particular about 190 - 250 nm. With particles having a particles size in the indicated range, colloidally stable dispersions are obtained.
• the concentration of the doped polymer in the liquid phase can vary in broad ranges depending on the conductive complex and on the concentration of the free sulphonic acid groups. Generally, there is about 0.1 to 30 %, in particular about 0.5 to 10 %, by weight of doped polymer in the solution.
• the sulphonated polymer contains about 0.01 to 1.5, in particular about 0.6 to 1.0, free sulphonic acid groups per repeating unit in the solution phase.
• the sulphonation agent is a polymer, which contains aromatic repeating units forming a rigid or semi-rigid backbone to form a sulphonated polymer which contains 0.1 to 0.95 sulphonic acid groups per repeating units of the polymer.
• suitable polymers include poly(phenylene oxide), (poly(3, 5 -dimethyl- 1,4- phenylene oxide) and poly(phenylene sulphide) which are sulphonated as known per se, e.g. by contacting the polymer in a non-polar solvent with a sulphonating agent such as fuming sulphuric acid or mixtures of sulphuric acid and nitric acid.
• a sulphonating agent such as fuming sulphuric acid or mixtures of sulphuric acid and nitric acid.
• Other examples include aromatic polyimides, polymers of the Kevlar® type and poly(ether-ether-ketones). Before employing the sulphonated polymer as a doping agent it is purified and isolated from the sulphonation medium.
• a solution of a sulphonated polymer is first prepared, containing about 0.1 to 15 %, in particular about 0.2 to 5 %, by mass of the sulphonated polymer in a polar solvent and the polymer is then contacted in the polar solvent with about 1:100 to 100:1, preferably about 1:10 to 5:1, in particular about 1:5 to 1:1, parts by weight of monomers of the inherently conductive polymer backbone.
• the monomers are polymerized in the presence of an oxidative catalyst, such as various persulphate compounds (e.g. ammonium persulphate, APS).
• the in situ polymerization is carried out, preferably under agitation, in the presence of the sulphonated polymer at a temperature in excess of -20 0 C up to about 50 0 C, preferably at a temperature in the range of from -5 to 30 ° C, in particular at about 0 to 25 0 C.
• Polymerization is continued to obtain a conversion rate of at least 20 % (calculated from the weight of the monomers), in particular at least 40 %, preferably at least 60 % and advantageously at least 80 %.
• a conductive polymer complex is obtained in liquid phase, in which the polymeric components have a weight average molecular weight of about 1,000 to 250,000 g/mol, in particular about 5,000 to 100,000 g/mol, preferably about 10,000 to 50,000 g/mol.
• the conductivity of the polymer complexes varies over a large range depending on the components (the polymer/doping agent) and their concentrations. Generally, the conductivities are greater that 1*10 8 S/cm, in particular greater than 10 ⁇ 6 S/cm, and preferably about 1*10 4 to 10 S/cm, e.g. about 5*10 4 to 1*10 J S/cm.
• the present invention comprises the following steps for producing novel aqueous compositions:
• the novel compositions have several interesting uses.
• composition according to the present invention it is possible to coat plastic packaging materials with a conductive polymer at the ideal surface resistance range of 10 6 -10 9 ohm.
• inherently conductive polymers are permanently conductive and independent of the air humidity.
• such coatings are transparent.
• the products according to the present invention can be employed in applications that are used in explosive sensitive environment.
• lighting systems can be coated with a transparent layer of electrically conductive polymer, which prevents the formation of a dangerous discharge of the antistatic electricity.
• ESD paint and lacquer formulations for usage in antistatic applications are possible by using the invention in question.
• dust sensitive applications such as protective plastic films of displays, can be treated with the present water soluble inherently conductive polymer. Due to the reduced static electricity, dust formation would be less than for untreated plastic films.
• Another application area of the present invention is in the field of printed electronics.
• electronics relies strongly on silicon based semi-conductors.
• silicon based technology has clear restrictions.
• physical flexibility is required from the electronic component.
• silicon based technology this is difficult to achieve, due to the rigid nature of the silicon materials.
• silicon based electronics is complicated to manufacture, which increases the unit price of the components.
• water soluble inherently conductive polymers it is possible to print thin conductive patterns that are fully polymeric, flexible and semi-conductive.
• the thickness of the patterns can be 1 micrometre or less, typically about 1 to 1000 nm.
• Standard printing technologies can be used, such as gravure printing, screen printing and ink-jet printing. Therefore, high volume, low-cost production of electronic devices is possible. Examples of such printed electronics applications are various radio frequency identification (RFID) systems, memory elements, electrodes, supercondensators and photovoltaic devices, among others.
• RFID radio frequency identification
• water based solutions of inherently conductive polymers could be applied in sensors, such as biosensors, where electrical conductivity and its changes may be used as an indicator of e.g. chemical reactions, acidity changes and humidity changes.
• the present invention allows for the manufacture of such sensors by low-cost, commonly used printing methods.
• Poly(2,6-dimethyl-l,4-phenylene oxide) i.e. PDMPO was obtained from Aldrich (M w 220 000 g/mol) 1 .
• Polyphenylenesulfide (PPS) was obtained from Aldrich (M n 10 000 g/mol) 2 .
• Fuming sulfuric acid containing 20 % of SO 3 was obtained from Riedel-de Haen.
• Chloroform HPLC grade
• Methanol HPLC grade
• Concentrated sulphuric acid was obtained from AnalaR (sc. grade).
• Dialysis tubes used were Cellu sep MWCO 6000-8000 or 3500 provided by Orange Scientific.
• Sulphonation degree was determined from dry polymer by back titration with 0.100 M NaOH and 0.100 M HCl solutions.
• Poly(2,6-dimethyl-l,4-phenylene oxide) was sulphonated in chloroform solution using fuming sulfuric acid containing 20 % SO 3 as a sulphonating agent.
• 20 g of poly(2,6-dimethyl-l,4- phenylene oxide) was dissolved in 500 ml of dry chloroform in a two necked 1 L flask with mechanical stirring. Stirring speed was adjusted to 450 rpm. 10 ml of fuming sulfuric acid was added in the solution drop-wise at room temperature. The reaction was then continued for 18 hours. After 24 hours of total reaction time, 300 ml of methanol was added to cease the reaction and chloroform was removed using rotary evaporation.
• Sulphonated poly(2,6- dimethyl-l,4-phenylene oxide) was dialyzed against distilled water in Cellu sep-tubes MWCO 6000-8000 to remove remaining sulfuric acid. Dialysis was continued until the dialysis water remained neutral. The sulphonated polymer could not be precipitated from its water solution and was therefore recovered by lyophilization. Sulphonation ratio 3 was varied between 0.50 and 0.90 by changing the amount of fuming sulfuric acid and sulphonation time.
• the precipitated polymer dissolved completely to form totally transparent yellow-orange liquid in the tubes.
• Different degrees of sulphonation were achieved by varying the amount of fuming sulfuric acid in sulphonation as well as sulphonation time.
• Sulphonation degree was determined from dry polymer by back titration with 0.100 M NaOH and 0.100 M HCl solutions.
• Aniline and ammoniumpersulphate i.e. APS pro analysi grade were obtained from Merc and used as received.
• Aniline was polymerized by chemical polymerisation in a 250 ml round bottle flask equipped with a magnetic stirrer in room temperature (22 0 C). First, a predetermined amount of the selected doping acid was dissolved in 50 ml of 1 M hydrochloric acid and mixed for 2 hours. Next, a calculated amount of aniline was added to the reaction mixture and mixing was continued until the aniline had dissolved. Finally, calculated amount of APS dissolved in 20 ml of 1 M hydrochloric acid was added in the solution during a period of 1 h. Mixing was continued for 4 or 5 hours at room temperature. The product was purified by dialysis against water until the water remained neutral.
• Method A was used to prepare polyaniline complex with (PDMPO-SA9) with a sulphonation ratio of 0.80.
• PDMPO-SA9 polyaniline complex with (PDMPO-SA9) with a sulphonation ratio of 0.80.
• 0.400 g of PDMPO-SA9 was dissolved in 50 ml of 1 M hydrochloric acid in a 250 ml round bottomed flask with magnetic stirring. After 2 hours 0.164 g of aniline was dissolved in the solution. Then, 0.400 g of ammonium persulfate (APS) was dissolved in 20 ml of 1 M hydrochloric acid and added to the reaction solution during a period of 1 h. The reaction was allowed to continue for a further 4 hours and after that the solution was purified by dialysis against distilled water. Dialysis was continued until the water remained neutral and the dialyzed product was transferred to storage.
• APS ammonium persulfate
• Method A was used to prepare polyaniline complex with (PDMPO-SAlO) with a sulphonation ratio of 0.70.
• PDMPO-SAlO polyaniline complex with (PDMPO-SAlO) with a sulphonation ratio of 0.70.
• 0.400 g of PDMPO-SAlO was dissolved in 50 ml of 1 M hydrochloric acid in a 250 ml round bottomed flask with magnetic stirring. After 2 hours 0.148 g of aniline was dissolved in the solution. Then, 0.365 g of APS was dissolved in 20 ml of 1 M hydrochloric acid and added to the reaction solution during a period of 1 h. The reaction was allowed to continue for a further 4 hours and after that the solution was purified by dialysis against distilled water. Dialysis was continued until the water remained neutral and the dialyzed product was transferred to storage.
• Method A was used to prepare polyaniline complex with (PDMPO-SAl 1) with a sulphonation ratio of 0.60.
• PDMPO-SAl 1 was dissolved in 50 ml of 1 M hydrochloric acid in a 250 ml round bottomed flask with magnetic stirring. After 2 hours, 0.333 g of aniline was dissolved in the solution. Then, 0.814 g of APS was dissolved in 20 ml of 1 M hydrochloric acid and added to the reaction solution during a period of 1 h. The reaction was allowed to continue for another 4 hours and after that the solution was purified by dialysis against distilled water. Dialysis was continued until the water remained neutral and the dialyzed product was transferred to storage. Measured conductivity for PDMPO-SAl 1 -PANI-I is 4-10 "3 S cm "1
• Aniline was polymerized by chemical polymerisation in a 250 ml round bottle flask equipped with a magnetic stirrer at room temperature (22 0 C). First, a predetermined amount of the selected doping acid was dissolved in distilled water and mixed for 2 hours. Next, the calculated amount of aniline was added to the reaction mixture and mixing was continued until the aniline had dissolved. Finally, the calculated amount of APS dissolved in distilled water was added to the solution.
• Method A was used to prepare polyaniline complex with (PDMPO-SA12) with a sulphonation ratio of 0.80. Accordingly, 1.00 g of PDMPO-SA12 was dissolved in 40 ml of distilled water in a 250 ml round bottomed flask with magnetic stirring. After 2 hours 0.331 g of aniline was dissolved in the solution. Then, 0.810 g of APS was dissolved in 10 ml of distilled water and added to the reaction solution in a period of 1 h. The reaction was allowed to continue for another 4 hours and after that the solution was purified by dialysis against distilled water. Dialysis was continued for 20 h and the dialyzed product was transferred to storage.
• Example 4 was repeated, but the amount of aniline was changed to 0.248 g and the amount of APS to 0.607 g.
• Example 4 was repeated, but the amount of aniline was changed to 0.414 g and the amount of APS to 1.013 g.
• the product obtained was a viscous solution.
• Example 4 was repeated, but the amount of aniline was changed to 0.496 g and the amount of APS to 1.213 g.
• the product obtained was a viscous solution.
• Aniline was polymerized by chemical polymerisation in a 250 or 500 ml round bottle flask equipped with a magnetic stirrer in room temperature (22 0 C). First, the calculated amount of aniline was dissolved in a predetermined amount of the selected doping acid solution, which was obtained from the dialysis procedure without lyofilization. Finally, the calculated amount of APS dissolved in distilled water was added to solution.
• Method C was used to polymerize polyaniline complex with (PDMPO-SA12) with a sulphonation ratio of 0.50.
• PPS-SA3 in the form of an aqueous solution was placed in a 250 ml round bottomed flask equipped with magnetic stirring, and 0.268 g of aniline was dissolved in the solution.
• 0.656 g of APS was dissolved in 5 ml of distilled water and added to the reaction solution within an hour. The reaction was allowed to continue for another 4 hours and after that the solution purified by dialysis against distilled water. Dialysis was continued for 10 hours and the dialyzed product was transferred to storage.
• Aniline was polymerized by chemical polymerisation in a 1000 ml reactor equipped with a cooling mantel and a magnetic stirrer at 0 0 C. First, the calculated amount of aniline was dissolved in the selected doping acid solution, which was obtained via sulphonation method B. Finally, the calculated amount of APS was dissolved in distilled water and added to the solution.
• Method D was used to prepare polyaniline complex with (PDMPO-SA23k) with a sulphonation ratio of 0.90. Firstly, 5.00 g (107 ml) of PDMPO-SA23k as aqueous solution was placed in a 1000 ml round bottomed reactor equipped with a cooling mantel and a magnetic stirrer. Then, 1.54 g of aniline was added to the solution. Next, APS (4.15 g) was dissolved in 20 ml of distilled water and added to the reaction solution within one hour. The reaction was continued for another 16 hours, after which the solution was purified by dialysis against distilled water. Dialysis was continued for 10 hours and the dialyzed product was transferred to storage.
• Aniline was polymerized by chemical polymerisation in a 250 ml round bottle flask equipped with a magnetic stirrer at room temperature (22 0 C). First, a predetermined amount of the selected doping acid was dissolved in methanol and mixed for 1 hour. Next, a calculated amount of aniline was added to the reaction mixture and mixing was continued until aniline was fully dissolved. Finally, calculated amount of APS was dissolved in water and added to the solution drop-wise. Mixing was continued for overnight (16 h) at room temperature. The product was purified by dialysis against methanol until the solution remained neutral.
• Method E was used to prepare polyaniline complex with (PDMPO-SAl 5) with a sulphonation ratio of 0.95. Firstly, 2.00 g of PDMPO-SAl 5 was dissolved in 40 ml of methanol and placed in a 250 ml round bottomed flask equipped with a magnetic stirrer. Then, 0.65 g of aniline was added to the solution. Next, APS (1.75 g) was dissolved in 10 ml of distilled water and added to the reaction solution within an hour. The reaction was continued for another 16 hours and after that the solution was purified by dialysis against methanol. Dialysis was continued for 10 hours and the dialyzed product was transferred to storage.
• Aniline was polymerized and purified as in example E, except the solvent used was ethanol instead of methanol.
• Method F was used to prepare polyaniline complex with (PDMPO-SA20) with a sulphonation ratio of 0.70.
• PDMPO-SA20 polyaniline complex with (PDMPO-SA20) with a sulphonation ratio of 0.70.
• 2.00 g of PDMPO-SA20 was dissolved in 40 ml of ethanol and placed in a 250 ml round bottomed flask equipped with a magnetic stirrer. Then, 0.56 g of aniline was dissolved in the solution.
• APS (1.75 g) was dissolved in 10 ml of distilled and added to the reaction solution within an hour. The reaction was continued for another 16 hours and after that the solution was purified by dialysis against methanol. Dialysis was continued for 10 hours and the dialyzed product was transferred to storage.

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