Collect. Czech. Chem. Commun. 1992, 57, 349-356

Determination of the Tacticity of Poly(methyl methacrylate) by Hydrolysis Rate Measurements

František Mikeš and Jan Pecka

Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, 162 06 Prague 6


The rate of hydrolysis of poly(methyl methacrylate) increases with the content of meso(isotactic) diads in the polymer. The increase in the rate of hydrolysis of isotactic polymers is due to an intramolecular nucleophilic attack by the adjacent carboxylic ion on the carbonyl carbon atom in the ester group. An analysis of the content of sequences of variously arranged ester and carboxylic groups shows that the hydrolysis of s-poly(methyl methacrylate) is a random process, while i-poly(methyl methacrylate) is hydrolyzed gradually (by zip mechanism), starting from the carboxylate group formed by an external attack by hydroxylic ions. The kinetic data thus obtained cannot be interpreted in terms of a simple kinetic model. The tacticity of poly(methyl methacrylate) may be estimated from the dependence of the rate of hydrolysis on the content of meso diads determinated by NMR spectrometry. The rate of hydrolysis depends not only on the tacticity of the polymer, but probably also on its configurational sequence statistics.