Summary: Vinylphosphonic acid is polymerized at 80 °C by free radical polymerization to give a high‐molecular‐weight polymer ( of 6.2 × 104) as determined by static light scattering. High‐resolution NMR spectroscopy is used to gain microstructure information. Information based on tetrad probabilities is utilized to deduce an almost atactic configuration. In addition, 13C NMR spectroscopy gives evidence for the presence of head‐to‐head and tail‐to‐tail links. Refined analysis of the 1H NMR spectra allows for the quantitative determination of the fraction of these links (23.5% of all links). Experimental evidence suggests that the polymerization proceeds via cyclopolymerization of the vinylphosphonic acid anhydride as an intermediate. Titration curves indicate that high‐molecular‐weight poly(vinylphosphonic acid) PVPA behaves as a monoprotic acid.
Radical polymerization of vinylphosphonic acid proceeds by cyclopolymerization of its anhydride.
of 6.2 × 104) as determined by static light scattering. High‐resolution NMR spectroscopy is used to gain microstructure information. Information based on tetrad probabilities is utilized to deduce an almost atactic configuration. In addition, 13C NMR spectroscopy gives evidence for the presence of head‐to‐head and tail‐to‐tail links. Refined analysis of the 1H NMR spectra allows for the quantitative determination of the fraction of these links (23.5% of all links). Experimental evidence suggests that the polymerization proceeds via cyclopolymerization of the vinylphosphonic acid anhydride as an intermediate. Titration curves indicate that high‐molecular‐weight poly(vinylphosphonic acid) PVPA behaves as a monoprotic acid. 