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

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.