The kinetics of acid hydrolysis of polymeric ketone acetals

The kinetics of acid hydrolysis of poly[(2,2‐dimethyl‐1,3‐dioxolane‐4‐yl)methyl methacrylate] and of its copolymers with methyl methacrylate in homogeneous phase was investigated by means of mass spectrometry using perdeuterated acetone as the internal standard. It was found that under conditions of a pseudomonomolecular reaction the homopolymer is capable of an acceleration process with respect to the splitting‐off of acetone according to the content of the syndiotactic dyads. The respective rate constants K0 and K1 were calculated. Characterization of the steric situation by means of models of polymeric ketonacetals and the absence of acceleration in the case of copolymers even containing only a small amount of methyl methacrylate units lead to the conclusion that the reported phenomenon is due to steric effects combined with a neighbouring group effect.