Optimization of Polymerization Conditions of Furan with Aniline for Variable Conducting Polymers

Abstract

A high-throughput multiparameter optimization of chemical oxidative polymerization conditions has been developed for a facile synthesis of furan homopolymers and furan/aniline copolymers using a combinatorial method. The polymerization yield, molecular structure, and properties of the polymers would be optimized against typical polymerization parameters, including oxidant species, medium species, temperature, oxidant/monomer ratio, monomer concentration, dopant concentration, and furan/aniline comonomer ratio. The electrical conductivity, lead ion adsorptivity, chemical resistance, and thermal behavior of the polymers were also elaborated. It is found that only a combination of FeCl(3) and nitromethane as oxidant and medium, respectively, is appropriate for the furan homopolymerization. The homopolymerization yield increases consistently with an increase in the monomer concentration from 0.05 to 0.2 M and the FeCl(3)/furan molar ratio from 0.25 to 1.25. Although the as-prepared polyfuran exhibits very low conductivity, down to 10(-11) S cm(-1), the HCl- and HClO(4)-doped polyfurans possess much higher conductivities of 9.2 x 10(-8) and 2.38 x 10(-5) S cm(-1), respectively. In addition, the conductivity of the furan/aniline copolymer rises steadily with increasing aniline content, although the copolymerization yield shows a minimum at the furan/aniline molar ratio of 60/40, which is evidence of the occurrence of a real copolymerization between the furan and aniline monomers. The difficulty of synthesizing conducting polyfuran could be overcome to some extent by the polymerization in an appropriate condition optimized in this study. Particularly, the difficulty of synthesizing poly(furan-co-aniline) having much higher conductivity than the polyfuran would be largely conquered by chemical oxidative copolymerization of furan with aniline.

Simple synthesis of conducting poly(2-aminothiazole) with high molecular weight

“…When a relatively highly concentrated FeCl 3 (20 mol%) was used, the polymer yields were decreased with extending polymerization time (>48 h). This coincides well with the phenomenon usually found in chemical syntheses of polyaniline and polypyrrole [21] because the polymeric chains of P2AT likely decomposed through peroxidative degradation with increasing polymerization time, and then the polymer yield decreased [31,32].…”

Electrochemical synthesis of polymer based on 4-(2-furyl) benzenamine: Electrochemical properties, characterization and applications

“…Aniline/furan copolymers with broad conductivity values developed with the help of a chemical oxidative polymerization of aniline/furan mixtures in CH 3 NO 2 were reported by Li et al [37]. Results from IR spectra and DSC thermogram showed that the polymer formed in solution including a mixture of two monomers is a real copolymer instead of mixture of two homopolymers [37]. Various composites of PFu and halogenated PANI or poly(o-toluidine) in order to improve the processibility of PFu have been prepared by Gonzalez-Tejera et al [38].…”

“…PFBA was chemically synthesized by oxidative polymerization of FBA in CHCl 3 and preliminary studies were carried out to characterize the polymer by UV-vis and IR spectroscopies and cyclic voltammetry technique [36]. Aniline/furan copolymers with broad conductivity values developed with the help of a chemical oxidative polymerization of aniline/furan mixtures in CH 3 NO 2 were reported by Li et al [37]. Results from IR spectra and DSC thermogram showed that the polymer formed in solution including a mixture of two monomers is a real copolymer instead of mixture of two homopolymers [37].…”

On the oligomerization mechanism of Brønsted acid-catalyzed conversion of furans to diesel-range fuels

“…Corma and co-workers further exemplified the "oligomerization" of MF with a number of biomass-derived aldehydes and ketones; notably, aldehydes (e.g., pentanal) exhibited higher reaction rates than ketones (e.g., 2-pentanone) [2]. Besides the acid-catalyzed oligomerization, the polymerization of furans with oxidizing agents has been investigated [4][5][6]. During this reaction, the furan rings do not open and the furan chain (polyfuran) is dehydrogenated.…”