Poly(1,3-dioxolane) can be cleanly depolymerized to the monomer. As such, the 1,3-dioxolane system is a good one to study to learn about microscopic reversibility. Besides describing how to perform the reversible polymerization reaction, this paper also presents data on the pyrolysis-field ionization mass spectrometry (Py-f.i.m.s.) and g.p.c, of the polymer and n.m.r, characterization of the monomer and polymer. The Py-f.i.m.s. data indicate that unhydrolysed polymer fragments in a manner similar to the reverse of the polymerization sequence, i.e. the carbonium ion portion of the oxymethylene end group bites back on oxygen atoms in the backbone. Base-terminated polymer, on the other hand, appears to undergo mid-chain cleavage. A dominant peak in the Py-f.i.m.s. spectrum of either, however, corresponds to the protonated cyclic dimer, a 10-crown-4 ether. A sequestered proton structure is proposed for this protonated species.
Посилання на статтю:
Polymerization-depolymerization of 1,3-dioxolane / Joel M. Williams* and Hans-Rolf Schulten // Polymer. – 1992. – Vol 33. – P. 4630-4634.