Studies of the reactions of anhydrosulphites of α-hydroxy acids,part IX. thermal polymerisation of anhydrosulphites of α-hydroxy α-methyl carboxylic acids

The anhydrosulphites of a series of unsymmetrically substituted α-hydroxy acids have been prepared and their susceptibility to polymerisation by thermal decomposition studied. The first order rate determining ring scission process, leading to the formation of a reactive α-lactone intermediate which then undergoes spontaneous polymerisation, is the predominant mechanism even with substituents up to C₈. As the length of the n-alkyl substituent is increased the rate of decomposition and thus polymerisation increases until a plateau value is reached at around C₃. Further increase in substituent length decreases the rate of decomposition, an effect which is attributed to steric hindrance of the leaving group by long (C₆—C₈) substituents.