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• • 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
• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a method for synthesis of water-soluble and self-doped polyaniline graft copolymer. More particularly, tert-butoxycarbonyl - aminostyrene (BOC-AMS) was synthesized by reaction of aminostyrene (AMS) and di-tert-butyl dicarbonate ((BOC) 2 ), then copolymerized with sodium styrenesulfonate (SSNa) .
• BOC-AMS tert-butoxycarbonyl - aminostyrene
• SSNa sodium styrenesulfonate
• P (SSA-co-AMS) was prepared by elimination of the tert- butoxy carbonyl groups and aniline was graft copolymerized onto the P (SSA-co-AMS) which resulted in the novel water- soluble and self-doped poly (styrene-g-aniline) (PSSA-g- PANI) .
• Polyaniline is one of the extensively studied intrinsic conducting polymers and shows electrical conductivity after proton-doping or oxidation. It had been well known that polyaniline can be prepared with easiness, high yield and low cost of synthesis and also shows very high conductivity with excellent environmental stability in a conducting form.
• Poyaniline can be used in the advanced application such as secondary battery, light emitting diode, electrochromic materials and sensor because of it's excellent electrical and electrochemical and optical properties.
• polyaniline should be prepared in a film or processable form.
• development of water-soluble polymers becomes important when commercial applications are considered.
• few solution processes have been reported because conducting polymers based on polyaniline are not soluble in common solvent due to the ⁇ - ⁇ interaction between the rigid polyaniline backbone.
• processable polyaniline that is soluble in organic solvent or water was developed by virtue of the advance in the research on solution process.
• Base form of polyaniline (emeraldine base) can be processed in solvent such as strong Lewis-acid, like N- methyl pyrrolidone (NMP) (Tzou, K.T. and Gregory, R.V. Synth. Met.
• NMP N- methyl pyrrolidone
• Conducting forms of polyaniline can be processed in a polar or non-polar solvent by using the acidic dopant such as dodecylbenzene sulfonic acid or camphorsulfonic acid (Cao, Y., Smith, P. and Heeder, A.J. Synth. Met. 1992, 48,91) .
• the method for the preparation of water-soluble polyaniline has been also developed.
• the dialysis was conducted to purify the resulted polyaniline, but it takes much time and there is a doubt on the degree of purity.
• the excess water also should be extracted for the preparation of desired concentration of water-soluble polyaniline aqueous solution.
• the electrochemical properties such as reversible oxidation/reduction and the stability during the potential swap cycle is very important when film or coatings of the solution-processed polyaniline are used in electrochemical applications.
• the most important factor that determines such properties is the ionic conductivity of the film.
• the diffusion rate of ions has effects on the reversibility of oxidation/reduction and the length of life.
• the present invention is the preparation method for novel water-soluble and self-doped polyaniline graft copolymer, which is represented by the following formula 1. [Formula 1]
• the figure 1. Synthetic route for poly (styrenesulfonic acid-g-polyaniline (PSSA-g-PANI)
• the figure 2. FTIR spectra of (a) P (SSNa-co-BOC-AMS) , (b) P (SSA-co-AMS) and (c) PSSA-g-PANI, where Q, B and op denote the quinoid ring, benzenoid ring and out-of-plane, respectively.
• the figure 3. 1 H NMR spectra of (a) P (SSNa-co-BOC-AMS) , (b) P (SSA-co-AMS) in DMSO solution and (c) PSSA-g-PANI in D 2 0 solution.
• UV-visible spectra of PSSA-g-PANI (a) self-doped state in aqueous solution and (b) de-doped state in aqueous NH 4 0H(1 M) solution Best Mode for Carrying Out the Invention
• the objective of the present invention is the preparation of water-soluble and self-doped conducting polyaniline graft copolymer by graft copolymerization of aniline onto poly (styrenesulfonic acid) backbone.
• BOC-AMS tert-butoxycarbonyl- aminostyrene
• P (SSNa-co-BOC-AMS) was synthesized by copolymerization of BOC-AMS and sodium styrenesulfonate (SSNa) , as described in the following reaction formula 2.
• P (SSA-co-AMS) was prepared by elimination of the BOC groups in P (SSNa-co-BOC-AMS) .
• PSSA-g-PANI structural formula 1 was synthesized by grafting of aniline onto the P (SSA-co-AMS) , as described in the following reaction formula 4.
• the entire experimental procedure represents in the figure 1 as chemical formula.
• the preparation method for the synthesis of BOC-AMS in the present invention is explained concretely as following.
• the synthesis of the BOC-AMS was carried out in order to reduce the transfer of lone-pair electron of amino group down to the vinyl group in para position and hinder any interaction either of the free radical initiator or of the growing chain. Indeed, aminostyrene submitted to homopolymerization or copolymerization with styrene by free radical initiator, only low molar mass products could be obtained in fairly poor yield.
• AMS and (BOC) 2 in dioxane were reacted in the water/ice bath.
• ANI 0.2 g
• 20 ml of ammonium persulfate (0.49 g) /HCl aqueous solution (IM) is dropwise added at 0 °C .
• IM ammonium persulfate
• a dark green solution was obtained and then filtered.
• the filtered solution was further purified by dialysis using a semipermeable membrane (molecular weight cutoff, 3500) .
• the chemical structure of PSSA-g-PANI obtained in the present invention was identified by FT-IR and ⁇ NMR analysis, shown in Figure 2 and Figure 3, respectively.
• the UV-visible spectrum of PSSA-g-PANI shows that the polaron band transitions take place at 420 nm and 770 nm, as shown in Figure 6 (a) , which indicates that the PSSA-g- PA ⁇ I is in self-doped state.
• the two peaks at 420 and 770 nm disappear and a new strong absorption peak appears at 550 nm due to ⁇ - ⁇ * transition of quinoid rings in PA ⁇ I, as shown in Figure 6(b) .
• the PSSA-g-PANI so obtained is completely soluble in water and polar solvent such as DMSO even after prolonged high vacuum drying to eliminate residual water.
• the Tyndall effect isn't also observed when re-dissolved in water.
• the present invention is described in detail by examples. It should however be borne in mind that these examples are not the limit of the present invention but just specific examples.
• Example 1 Synthesis of water-soluble and self-doped polyaniline graft copolymer (change of the backbone molecular weight ) P(SS ⁇ a-co-BOC-AMS) was synthesized by copolymerization of SSNa and BOC-AMS.
• SSNa 5 g
• BOC-AMS 0.5 g
• AIBN 0.01 ⁇ 0.2g
• the product was precipitated into acetone, filtered, washed several times with acetone, and dried in vacuum oven at 60 °C for 24 h.
• Example 2 Synthesis of water-soluble and self-doped polyaniline graft copolymer (change of the grafting length) P (SSNa-co-BOC-AMS) was synthesized by copolymerization of SSNa and BOC-AMS. SSNa (5 g) , BOC-AMS (0.5 g) , and AIBN (O.lg) are dissolved in 60 ml of DMSO and polymerized at 80 °C for 15 h under N2 atmosphere.
• ANI is first added to the P (SSA-co-AMS) solution over the period of 0.5 h with stirring with the ANI/P (SSA-co-AMS) molar ratio from 0.1 to 100 and then 20 ml of ammonium persulfate/HCl aqueous solution (IM) is dropwise added at 0 °C.
• IM ammonium persulfae/ANI
• the obtained graft copolymers have anline units about 1 ⁇ 400 as an average grafting lengths and didn't be solubilized in water when aniline unit are over 20.
• the sulfonic acid groups that participated in water-solubility decreased and it became insoluble .
• Example 5 Electrochemical synthesis of water-soluble and self- doped polyaniline graft copolymer
• P (SSNa-co-BOC-AMS) was spin- coated on a Pt disc electrode.
• the electrochemical polymerization of aniline onto P (SSNa-co-BOC-AMS) was performed by applying intended potential to the electrode using potentiostat (EG&G 273A) .
• EG&G 273A potentiostat
• a standard three-electrode cell consists of a disk-type Pt working electrode (diameter, 1cm) , a plate-type Pt counter electrode, and an aqueous sodium chloride saturated calomel electrode (SCE) as a reference electrode was employed.
• SCE sodium chloride saturated calomel electrode
• the electrolyte solution was 1.0 M aqueous HCl in DMF/Water mixture. After anline was added to the solution, N 2 gas was purged for Ih.
• the potential range for electrochemical polymerization and the scanning rate are -0.2 ⁇ 1.0V (vs. SCE) and 50mV/sec, respectively.
• Example 6 synthesis of water-soluble and self-doped polyaniline graft copolymer (the facile synthesis method without dialysis procedure)
• the water-soluble polyaniline prepared by above methods can't be extracted from the reaction solution after synthesis. This is because residual product and reagent that remains unreacted in the solution is very difficult to separate from water.
• the dialysis was conducted to purify the prepared polyaniline, but it takes much time and there is a doubt on the degree of purity.
• the excess water also should be removed for the preparation of desired concentration of water-soluble polyaniline aqueous solution. If the graft copolymer is precipitated and all the other agents are dissolved in solvent after synthesis, the products can be separated easily by filteration.
• the aceonirile/water (8:2) was chosen in order to satisfy these requirements .
• the precursor for the graft copolymerization, P (SSNa-co-BOC-AMS) , monomer, and oxidant were completely dissolved in this co-solvent, however PSSA-g-PANI were not.
• ANI (0.2 g) is first added to the P (SSA-co-AMS) solution over the period of 0.5 h with stirring, and then 20 ml of ammonium persulfate (0.49 g) /HCl aqueous solution (IM) is dropwise added at 0 °C. After 6 h of reaction, a dark green solution was obtained and then filtered. PSSA-g-PANI was precipitated and remained on the filterpaper, while all the others got through the filter paper. After washed with acetone several times, PSSA-g-PANI was vacuum-dried in oven at 30 °C for 24 h. Even after elimination of the residual water, PSSA-g-PANI was completely dissolved in water. Synthesis of polyaniline is impossible in organic- solvent. Thus in this example, the synthesis of polyaniline was accomplished with the proper ratio of organic solvent/water co-solvent. The proper ratio (8:2) was chosen for the selective precipitation of graft copolymer.
• the water-soluble and self-doped conducting polyaniline graft copolymer has the merit that water-soluble backbone moieties (sulfonic acid groups) , which do not participate in self-doping, make the polymer soluble in water or polar organic solvent such as dimethyl sulfoxide (DMSO) .
• the polymeric dopant backbone pol (styrenesulfonic acid)
• the water-soluble and self- doped conducting polyaniline invented here will become a basic material for advanced applications such as electrode, EMI shielding, static electricity dissipation, metal anti- corrosion, electrochromic materials, sensor, functional film and marine-fouling prevention.

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