Polymerization of anilines by the use of copper(II) perchlorate as an oxidative coupling agent

Inoue, Motomichi; Brown, Francisco; Muñoz, Iliana C.; Muñoz, Fca. Ofelia

doi:10.1007/bf00302607

Cited by 8 publications

(2 citation statements)

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“…The M̄ w of PANI−Cu/w is ca. 2.5 times lower than that one of ES−PANI but is in agreement with the value reported for the polymer synthesized using Cu(II) perchlorate in acetonitrile medium . The M̄ w value of PANI−Cu/ACN is 16 900, considering aniline as a mero, the polymer chain has ca.…”

Section: Resultssupporting

confidence: 88%

“…In PANI chemical synthesis, persulfate ions (S 2 O 8 2- ) in aqueous acid solutions are commonly used as oxidizing agent and the chain structure involves the monomer in a head-to-tail sequence. , The isolated green polymer is the well-known PANI in the emeraldine salt form (ES−PANI). Polymerization of aniline can also be done in nonaqueous medium such as acetonitrile and using Cu(II) as oxidant. − In these experimental conditions, the structure of the polymer has been recognized to be similar to ES−PANI, with small amount of branched structure (from ortho coupling). , However, these materials have not been characterized by resonance Raman technique, and its employment can give new insights about the polymer structure and the role of distinct synthetic conditions.…”

Section: Introductionmentioning

confidence: 99%

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Spectroscopic Characterization of Polyaniline Formed by Using Copper(II) in Homogeneous and MCM-41 Molecular Sieve Media

2005

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This work emphasizes the important role of the synthetic parameters in the structure of the polymeric material obtained in the aniline polymerization. The polymers formed by the oxidative polymerization of aniline by copper(II) ions in acidic aqueous solution, acetonitrile/water medium, and also copper(II) acetate complex encapsulated into MCM-41 molecular sieve were characterized by resonance Raman spectroscopy using three exciting laser lines and other techniques such as UV−vis, FTIR, and XANES (Nitrogen K edge). Additionally the products were investigated by thermogravimetric analysis and powder X-ray diffraction. When Cu(II) ions in acidic aqueous medium are used, emeraldine salt (ES−PANI) is formed through the usual head-to-tail polymerization mechanism, while in acetonitrile/water medium a polymer is observed having mainly phenazine-like rings, quinonediimine, and/or phenylenediamine segments in the chains, suggesting that a distinct mechanism is operating. The average molecular weights of the free polymers synthesized in water and in acetronile/water were, respectively, ca. 37 300 and 16 900 Da. The encapsulated polymer synthesized in Cu(II)-MCM-41 is a polymeric mixture of (i) ES−PANI and (ii) the polymer obtained when this metal cation was used as oxidant in acetonitrile/water medium. All the characterization data were compared to those ones obtained for standard free polyaniline and also for the encapsulated polymer into mesoporous MCM-41 formed by using persulfate in acidic aqueous medium as oxidant.

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Section: Resultssupporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Spectroscopic Characterization of Polyaniline Formed by Using Copper(II) in Homogeneous and MCM-41 Molecular Sieve Media

2005

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Synthesis and polymerization of 2‐alkylanilines

Bodalia

Stern

Batich

et al. 1993

J. Polym. Sci. A Polym. Chem.

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2‐Alkylanilines with alkyl groups in the range of 4–15 carbon atoms were synthesized via a known method as well as via a more general path which should allow the introduction of a larger variety of substituted alkyl groups into the ortho position of aniline, e.g., alkenyl or OH, NH2, COOH, and phenyl functionality. Polymerization was found to be achievable according to a method previously described for unsubstituted aniline, i.e., chemically with Cu(ClO4)2 · 6H2O in acetonitrile. Intrinsic viscosities of the obtained poly(2‐alkylaniline)s lay between 0.10 and 0.26 dL/g (97% H2SO4 at 30°C). The dc conductivity of the HCl salts decreased with increasing length of the alkyl side chains from 1 S/cm (polyaniline) over 3 X 10−4 S/cm [poly(2‐butylaniline)] to 1 X 10−6 S/cm poly(tridecylaniline). Further characterization of the polymers were performed by means of UV/VIS/NIR‐and‐IR spectroscopy, in dilute solutions or as KBr pellets, respectively, and by solubility tests. © 1993 John Wiley & Sons, Inc.

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