OXIDIZED AND REDUCED POLY(2,5-DI-(-2-THIENYL)-PYRROLE) - SOLUBILITIES, ELECTRODISSOLUTION AND MOLAR-MASS

被引:29
作者
BRILLAS, E
CARRASCO, J
FIGUERAS, A
URPI, F
OTERO, TF
机构
[1] UNIV BARCELONA, FAC QUIM, DEPT ENGN QUIM & MET, E-08028 BARCELONA, SPAIN
[2] UNIV BARCELONA, FAC QUIM, DEPT QUIM ORGAN, E-08028 BARCELONA, SPAIN
[3] UNIV BASQUE COUNTRY, FAC QUIM, DEPT CIENCIA & TECNOL POLIMEROS, ELECTROQUIM LAB, E-20080 SAN SEBASTIAN, SPAIN
关键词
POLY(2,5-DI-(-2-THIENYL)-PYRROLE); ELECTRODISSOLUTION; SOLUBILITY;
D O I
10.1016/0022-0728(95)04019-K
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
Oxidized poly(2,5-di-(-2-thienyl)-pyrrole was synthesized electrochemically from a 5 to 20 mM monomeric solution in 0.1 M LiClO4 + acetonitrile (ACN). The electrochemical behaviour of films was studied in 0.1 M LiClO4 aqueous solution, where an insoluble reduced form was found. Solubilities of both oxidized and reduced states were determined in DMSO, acetone and ACN. Their densities and electrical conductivities were also obtained. The solubility of the reduced form is about 15 times higher in DMSO and ACN than that of the oxidized form. The oxidized polymer is insoluble in ACN solutions of perchlorate salts. The high solubility of the reduced state in this medium allows a quantitative electrodissolution of the polymer following the reduction process. Results from electrochemical experiments, ultramicrogravimetry and elemental analysis indicate an average presence of 0.65 ClO4- ions per monomeric unit incorporated in the oxidized polymer. Both states contain soluble oligomers with from two to six monomeric units, as detected by mass spectrometry (fast atom bombardment). The molecular mass of these oligomers indicates a loss of two protons per monomer incorporated in the polymer, in agreement with an electropolymerization mechanism involving polycondensation of radicals.
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收藏
页码:55 / 61
页数:7
相关论文
共 15 条
[1]   ANODIC ELECTROSYNTHESIS AND CATHODIC ELECTRODISSOLUTION OF POLY(2,5-DI-(2-THIENYL)PYRROLE) - A NEW WAY OF PROCESSIBILITY [J].
CARRASCO, J ;
FIGUERAS, A ;
OTERO, TF ;
BRILLAS, E .
SYNTHETIC METALS, 1993, 61 (03) :253-258
[2]   OPTICAL, ELECTRICAL AND ELECTROCHEMICAL PROPERTIES OF HETEROAROMATIC COPOLYMERS [J].
FERRARIS, JP ;
HANLON, TR .
POLYMER, 1989, 30 (07) :1319-1327
[3]   SPECTROELECTROCHEMICAL STUDY OF POLYPYRROLE FILMS [J].
GENIES, EM ;
BIDAN, G ;
DIAZ, AF .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1983, 149 (1-2) :101-113
[4]   SYNTHESIS, ELECTRICAL-CONDUCTIVITY AND ELECTRON-PARAMAGNETIC-RESONANCE SPECTROSCOPY OF POLYMERS DERIVED FROM NOPF6-DOPED XYZ-TRIHETEROCYCLES BASED ON PYRROLE, FURAN AND THIOPHENE [J].
JOSHI, MV ;
HEMLER, C ;
CAVA, MP ;
CAIN, JL ;
BAKKER, MG ;
MCKINLEY, AJ ;
METZGER, RM .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1993, (06) :1081-1086
[5]   SYNTHESIS, ELECTROCHEMICAL POLYMERIZATION AND PROPERTIES OF POLY(2,5-DI-(2-THIENYL)-PYRROLE) [J].
MCLEOD, GG ;
MAHBOUBIANJONES, MGB ;
PETHRICK, RA ;
WATSON, SD .
POLYMER, 1986, 27 (03) :455-458
[6]   A MECHANISTIC STUDY OF THE ELECTROCHEMICAL OXIDATION OF 2,5-BIS(2-THIENYL)PYRROLES [J].
NIZIURSKIMANN, RE ;
SCORDILISKELLEY, C ;
LIU, TL ;
CAVA, MP ;
CARLIN, RT .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (03) :887-891
[7]   ELECTROCHEMOMECHANICAL PROPERTIES FROM A BILAYER - POLYPYRROLE NONCONDUCTING AND FLEXIBLE MATERIAL ARTIFICIAL MUSCLE [J].
OTERO, TF ;
ANGULO, E ;
RODRIGUEZ, J ;
SANTAMARIA, C .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1992, 341 (1-2) :369-375
[8]   ELECTROCHEMICAL OXIDATION OF 2,5-DI-(-2-THIENYL)-PYRROLE IN ACETONITRILE - CATHODIC STRIPPING OF THE ELECTROGENERATED CONDUCTING POLYMER [J].
OTERO, TF ;
CARRASCO, J ;
FIGUERAS, A ;
BRILLAS, E .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1994, 370 (1-2) :231-239
[9]  
OTERO TF, 1993, SOLID STATE IONICS, V63, P194
[10]  
OTERO TF, 1992, Patent No. 9200095