Abstract
The polymerization of methacrylic acid (MAA) along isotactic poly(2-vinylpyridine) (it-P2VP) template was studied by varying the template concentration at fixed initial monomer concentration (and vice versa) by calorimetric means. By applying a previously proposed generalized kinetic model, the various rate coefficients could be estimated and compared with those found previously with atactic (at)-P2VP as template. The smaller zip propagation coefficient points to a less favourable position between the template sites in it-P2VP. The larger rate coefficient of complexation of an initially formed poly(methacrylic acid) (PMAA) with it-P2VP is in agreement with the better complexation between PMAA and it-P2VP. This effect may also lead to a better shielding of the template radicals explaining thereby the smaller template termination coefficient. Finally, an explanation is offered for the extra retardation of termination at low template concentrations. Owing to charge build-up upon MAA binding, the separate coils expand and repel each other thus obstructing termination of growing template radicals.
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