Thermodynamic Parameters of the Oxidative Polymerization Catalyzed by Copper-Partially-quaternized Poly(vinylpyridine) Complexes

Hiroyuki Nishide, Toshio Nishiyama, Eishun Tsuchida

Research output: Contribution to journalArticle

Abstract

The electrostatic effect of Cu(H)-partially-quaternized poly(vinylpyridine) (QPVP) catalyst on the oxidative polymerization of 2, 6-xylenol was discussed in terms of the thermodynamic parameters of the catalysis and the shape of the QPVP complex. The intermediate complex is stable in the QPVP system from an enthalpy point of view (Table 2), and the Cu(I) complex is considered to be relatively stabilized by the strain of the QPVP-chain due to the electrostatic repulsion (Fig. 1). Activation entropy of the QPVP catalyst is large, and the larger entropy was observed in the QPVP complex having the more compact structure (Table 2, 3). In the QPVP-catalyzed oxidation of p-phenylenediamine, the chelate structure of the QPVP complex was destroyed by the coordination of the substrate.

Original languageEnglish
Pages (from-to)1565-1568
Number of pages4
JournalNippon Kagaku Kaishi / Chemical Society of Japan - Chemistry and Industrial Chemistry Journal
Volume1974
Issue number8
DOIs
Publication statusPublished - 1974

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Copper
Electrostatics
Entropy
Polymerization
Thermodynamics
Catalysts
Catalysis
Enthalpy
Chemical activation
Oxidation
Substrates
4-phenylenediamine
2,6-xylenol

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "The electrostatic effect of Cu(H)-partially-quaternized poly(vinylpyridine) (QPVP) catalyst on the oxidative polymerization of 2, 6-xylenol was discussed in terms of the thermodynamic parameters of the catalysis and the shape of the QPVP complex. The intermediate complex is stable in the QPVP system from an enthalpy point of view (Table 2), and the Cu(I) complex is considered to be relatively stabilized by the strain of the QPVP-chain due to the electrostatic repulsion (Fig. 1). Activation entropy of the QPVP catalyst is large, and the larger entropy was observed in the QPVP complex having the more compact structure (Table 2, 3). In the QPVP-catalyzed oxidation of p-phenylenediamine, the chelate structure of the QPVP complex was destroyed by the coordination of the substrate.",
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AU - Nishide, Hiroyuki

AU - Nishiyama, Toshio

AU - Tsuchida, Eishun

PY - 1974

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N2 - The electrostatic effect of Cu(H)-partially-quaternized poly(vinylpyridine) (QPVP) catalyst on the oxidative polymerization of 2, 6-xylenol was discussed in terms of the thermodynamic parameters of the catalysis and the shape of the QPVP complex. The intermediate complex is stable in the QPVP system from an enthalpy point of view (Table 2), and the Cu(I) complex is considered to be relatively stabilized by the strain of the QPVP-chain due to the electrostatic repulsion (Fig. 1). Activation entropy of the QPVP catalyst is large, and the larger entropy was observed in the QPVP complex having the more compact structure (Table 2, 3). In the QPVP-catalyzed oxidation of p-phenylenediamine, the chelate structure of the QPVP complex was destroyed by the coordination of the substrate.

AB - The electrostatic effect of Cu(H)-partially-quaternized poly(vinylpyridine) (QPVP) catalyst on the oxidative polymerization of 2, 6-xylenol was discussed in terms of the thermodynamic parameters of the catalysis and the shape of the QPVP complex. The intermediate complex is stable in the QPVP system from an enthalpy point of view (Table 2), and the Cu(I) complex is considered to be relatively stabilized by the strain of the QPVP-chain due to the electrostatic repulsion (Fig. 1). Activation entropy of the QPVP catalyst is large, and the larger entropy was observed in the QPVP complex having the more compact structure (Table 2, 3). In the QPVP-catalyzed oxidation of p-phenylenediamine, the chelate structure of the QPVP complex was destroyed by the coordination of the substrate.

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