Synthesis and properties of processable conducting copolymers from N‐ethylaniline with aniline

Copolymers were synthesized through the chemically oxidative polymerization of N-ethylaniline (EA) and aniline (AN) in five acid aqueous media. The polymerization yield, intrinsic viscosity, molecular weight, solubility, solvatochromism, electrical conductivity, and mechanical properties of the copolymer films were systematically studied through changes in the comonomer ratio, polymerization temperature, oxidant, oxidant/monomer ratio, and acid medium. Open-circuit-potential and temperature measurements of the polymerization solutions showed that the polymerization rate depended on the EA content, and the polymerization was an exothermic reaction. The resultant copolymers were characterized in detail with IR, ultraviolet-visible, and 1 H NMR spectroscopy, gel permeation chromatography, wide-angle X-ray diffractometry, and scanning electron microscopy. The reactivity ratios of the monomer pair were calculated from the 1 H NMR spectra of the copolymers formed at a low conversion. The polymers exhibited good solubility and interesting solvatochromism in most of the solvents and variable conductivity with the EA/AN ratio and doping state. The conductivity of the HCl-doped copolymers increased monotonically from 5.61 × 10 -7 to 2.55 x 10 1 S/cm with decreasing EA content from 100 to 0 mol % and showed a percolation transition between EA concentrations of 20 and 30 mol %. The EA/AN copolymers also had excellent film formability and flexibility together with high mechanical and oxygen-enriching properties.

[1]  Meifang Zhu,et al.  Facile synthesis and characterization of the copolymers and their pure nanoparticles from aniline with 4-sulfonic diphenylamine , 2004 .

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

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

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

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

[6]  Shu-ying Gu,et al.  Oxygen enrichment across blend membranes of bipyridine and ethyl cellulose , 2003 .

[7]  Shu-ying Gu,et al.  Oxygen enrichment from air through multilayer thin low-density polyethylene films , 2002 .

[8]  S. Umare,et al.  Chemical synthesis, characterization and transport properties of copolymer: Poly(aniline-co-m-methylaniline) , 2002 .

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

[10]  Yuliang Yang,et al.  Synthesis and air separation of soluble terpolymers from Aniline, Toluidine, and Xylidine , 2001 .

[11]  Meifang Zhu,et al.  Synthesis and characterization of pyrrole and anisidine copolymers , 2001 .

[12]  S. Umare,et al.  ELECTRICAL AND OPTICAL PROPERTIES OF CONDUCTING COPOLYMER: POLY(ANILINE-CO-N-ETHYLANILINE) , 2001 .

[13]  Xin-Gui Li,et al.  Actual air separation across multilayer composite membranes , 2000 .

[14]  A. MacDiarmid,et al.  A simple method to estimate the oxidation state of polyanilines , 2000 .

[15]  A. Falcou,et al.  General Access to ortho- and meta-Alkylanilines for the Synthesis of Polyanilines and Poly(Anilines-co-Substituted Anilines) , 2000 .

[16]  A. Falcou,et al.  Preparation of soluble N and o-alkylated polyanilines using a chemical biphasic process , 1999 .

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

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

[19]  Xin-Gui Li,et al.  Multilayer ultrathin‐film composite membranes for oxygen enrichment , 1997 .

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

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

[22]  K. Levón,et al.  Characterization and Solid-State Properties of Processable N-Alkylated Polyanilines in the Neutral State , 1994 .

[23]  M. Bernard,et al.  Electrochromic Performance of Polyaniline Films during Their Cycling in a pH 3 Electrolyte , 1994 .

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

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

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

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

[28]  A. Epstein,et al.  Polyaniline: Pernigranile, an isolable intermediate in teh conventional chemical synthesis of emeraldine , 1991 .

[29]  J. Langer N-substituted polyanilines: I. Poly(N-methylaniline) and related copolymers , 1990 .

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