Acidolysis of poly(4‐methyl‐1,3‐dioxolane)

Abstract

AbstractThe onset of decomposition of poly(4‐methyl‐1,3‐dioxolane) was lowered to 70°C by 0.1 wt% p‐toluene sulfonic acid from 170°C in the absence of acid to produce more than 81% yield of monomer. Protonation forms cyclic oxonium ion followed by depolymerization. Minor products are isomers of hydroxymethyl‐2‐hydroxyl‐2‐methyl ethyl ether and bis(2‐hydroxyl‐2‐methyl ethoxyl)methane from rearrangements of the oxonium ions. The first order rate constant of acidolysis of poly(4‐methyl‐1‐1,3‐dioxolane) is about 8.5 kcal mol−1, which is much smaller than about 17 kcal mol−1 for the acidolysis of poly(1,3‐dioxolane).