Abstract
Isotactic poly(2-vinylpyridine) was epimerized by the action of t-BuOK in DMSO solution. The course of the reaction was followed by 300 MHz 1H NMR as well as 20 and 90 MHz 13C NMR spectroscopy. It was found that the polymer epimerized until equilibrium was reached had essentially the same microstructure (σ∼0.5) as the polymer obtained by radical polymerization. Monte-Carlo simulation was used to calculate n-ad stereosequence distributions for the partially and completely epimerized polymers. Isotactic (mm) contents of the polymers measured from the methine proton and aromatic C2-carbon resonances, were in excellent agreement with those calculated by the Monte-Carlo method. The (mm)-aromatic C2-carbon resonance patterns were interpreted in terms of heptad stereosequence resonances. CSMP programming, coupled with an optimization routine was used to evaluate rate constants for the epimerization reaction. When studied at 90 MHz all aromatic carbon resonances were sensitive to stereosequence effects. Several of these were interpreted in terms of pentad resonances.
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Dworak, A., Freeman, W. & Harwood, H. Epimerization and NMR Spectra of Poly(2-vinylpyridine). Polym J 17, 351–361 (1985). https://doi.org/10.1295/polymj.17.351
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DOI: https://doi.org/10.1295/polymj.17.351
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