Facile synthesis and characterization of the copolymers and their pure nanoparticles from aniline with 4-sulfonic diphenylamine

Copolymer nanoparticles from aniline (AN) and 4-sulfonic diphenylamine (SDP) were simply synthesized for the first time by an oxidative precipitation polymerization with inorganic oxidants in an acidic aqueous medium without any external emulsifier or stabilizer. The polymerization yield, intrinsic viscosity, solubility, solvatochromism, electrical conductivity, and thermal stability of the copolymers were systematically studied through changes in the AN/SDP ratio, polymerization temperature, oxidant species, monomer/oxidant ratio, and acidic medium. The molecular structure of the copolymers was characterized with elemental analysis, IR, and ultraviolet–visible spectra. The polymers exhibited very good solubility in polar solvents, water, and NH4OH, and this was mainly attributable to the presence of sulfonic acid side groups. The electrical conductivity of the copolymers increased greatly, from 6.00 × 10−4 to 2.55 × 10−1 S/cm, with increasing AN content. The size of the copolymer particles, determined by laser particle analysis and atomic force microscopy (AFM), strongly depended on the polymer state and oxidant/monomer ratio. Pure dedoped particles of the AN/SDP (50/50) copolymer at an oxidant/monomer ratio of 1/2 exhibited minimum length/diameter ratios of 62/44 and 45/30 nm by AFM and transmission electron microscopy, respectively. The copolymers showed typical four-step weight-loss behavior in nitrogen and air and higher thermostability in nitrogen. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3380–3394, 2004

[1]  D. Zhao,et al.  A soluble ladder copolymer from m-phenylenediamine and ethoxyaniline , 2003 .

[2]  D. Zhao,et al.  Preparation and solubility of a partial ladder copolymer from p-phenylenediamine and o-phenetidine , 2003 .

[3]  Ursula Rammelt,et al.  Physical and electrochemical characterization of nanocomposites formed from polythiophene and titaniumdioxide , 2003 .

[4]  Xin-Gui Li,et al.  Novel multifunctional polymers from aromatic diamines by oxidative polymerizations. , 2002, Chemical reviews.

[5]  J. J. Ree,et al.  Synthesis and characterization of conducting poly(aniline‐co‐o‐aminophenethyl alcohol)s , 2002 .

[6]  Yuliang Yang,et al.  Preparation and characterization of soluble terpolymers from m‐phenylenediamine, o‐anisidine, and 2,3‐xylidine , 2001 .

[7]  Alan G. MacDiarmid,et al.  Polyaniline, a dynamic block copolymer: key to attaining its intrinsic conductivity? , 2001 .

[8]  Yuliang Yang,et al.  Oxidative copolymers of aniline with o-toluidine: Their structure and thermal properties , 2001 .

[9]  M. Whittingham,et al.  Synthesis and properties of the polyanisidines , 2001 .

[10]  Yuliang Yang,et al.  Soluble copolymers via oxidative polymerization of pyrimidylamine and anisidine , 2001 .

[11]  Sze‐Ming Yang,et al.  Syntheses of ethyl and ethoxy-substituted polyaniline complexes , 2001 .

[12]  T. Wen,et al.  In situ, UV-Vis spectroelectrochemical studies on the initial stages of copolymerization of aniline with diphenylamine-4-sulphonic acid , 2001 .

[13]  Yuliang Yang,et al.  Oxidative copolymerization of 2-pyridylamine and aniline , 2000 .

[14]  Ester Segal,et al.  Polymerization of aniline in the presence of DBSA in an aqueous dispersion , 1999 .

[15]  Xin-Gui Li,et al.  Kinetics of thermal degradation of thermotropic poly(p-oxybenzoate-co-ethylene terephthalate) by single heating rate methods , 1998 .

[16]  X. Jing,et al.  Polymerization of aniline in an aqueous system containing organic solvents , 1998 .

[17]  R. Holze,et al.  UV-VIS spectroelectrochemical detection of intermediate species in the electropolymerization of an aniline derivative , 1998 .

[18]  Mei-Rong Huang,et al.  Thermal degradation of cellulose and cellulose esters , 1998 .

[19]  H. Bai,et al.  Kinetics of thermal degradation of liquid‐crystalline aromatic polymers , 1998 .

[20]  Mu-Yi Hua,et al.  Structures and properties of the soluble polyanilines, N-alkylated emeraldine bases , 1998 .

[21]  C. Nicolini,et al.  The electrochromic response of polyaniline and its copolymeric systems , 1997 .

[22]  L. Dao,et al.  Electrochemical preparation and characterization of conducting copolymers: poly (aniline-co-N-butylaniline) , 1997 .

[23]  Mária Omastová,et al.  Electrical properties and stability of polypyrrole containing conducting polymer composites , 1996 .

[24]  S. Chen,et al.  Structure characterization of self-acid-doped sulfonic acid ring-substituted polyaniline in its aqueous solutions and as solid film , 1996 .

[25]  A. Diaz,et al.  Water-Soluble Conducting Copolymers of o-Aminobenzyl Alcohol and Diphenylamine-4-sulfonic Acid , 1994 .

[26]  S. Chen,et al.  Synthesis of Water-Soluble Self-Acid-Doped Polyaniline , 1994 .

[27]  Yen Wei,et al.  Monitoring the chemical polymerization of aniline by open-circuit-potential measurements , 1994 .

[28]  P. H. Kasai,et al.  Synthesis and properties of novel water-soluble conducting polyaniline copolymers , 1994 .

[29]  Alan J. Heeger,et al.  Counter-ion induced processibility of conducting polyaniline , 1993 .

[30]  L. Dao,et al.  Electrical and physical properties of new electrically conducting quasi-composites. Poly(aniline-co-N-butylaniline) copolymers , 1992 .

[31]  L. Dao,et al.  Synthesis, characterization, and properties of poly(N-alkylanilines) , 1992 .

[32]  M. Tsai,et al.  Mechanism of adenylate kinase. 10. Reversing phosphorus stereospecificity by site-directed mutagenesis , 1991 .

[33]  Arthur J. Epstein,et al.  Effect of sulfonic acid group on polyaniline backbone , 1991 .

[34]  Jinsong Tang,et al.  Infrared spectra of soluble polyaniline , 1988 .

[35]  Meifang Zhu,et al.  Synthesis and nitrosation of processible copolymers from pyrrole and ethylaniline , 2004 .

[36]  Meifang Zhu,et al.  Facile synthesis of highly soluble copolymers and sub-micrometer particles from ethylaniline with anisidine and sulfoanisidine , 2004 .

[37]  R. Holze,et al.  An in situ UV-vis spectroelectrochemical investigation of the initial stages in the electrooxidation of selected ring-and nitrogen-alkylsubstituted anilines , 1999 .

[38]  Koon Gee Neoh,et al.  POLYANILINE: A POLYMER WITH MANY INTERESTING INTRINSIC REDOX STATES , 1998 .

[39]  S. Armes,et al.  A novel N-substituted polyaniline derivative , 1993 .

[40]  G. Wnek,et al.  Synthesis and electrochemistry of alkyl ring-substituted polyanilines , 1989 .