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Synthesis of functionalized poly(1,3‐dioxolane)
Author(s) -
Franta E.,
Kubisa P.,
Kada S. Ould,
Reibel L.
Publication year - 1992
Publication title -
makromolekulare chemie. macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 0258-0322
DOI - 10.1002/masy.19920600113
Subject(s) - oxonium ion , dimethoxymethane , dioxolane , chemistry , monomer , polymerization , propylene oxide , methanol , polymer chemistry , diol , double bond , triol , copolymer , organic chemistry , ethylene oxide , ion , polymer
Abstract Classical initiation induces polymerization through cyclic tertiary oxonium ions which are responsible for the formation of an important quantity of cyclic oligomers. The activated monomer mechanism, i.e. polymerization in the presence of a diol, has been successful in the case of some substituted oxiranes such as epichlorohydrine and propylene oxide. It has also been used in the case of cyclic acetals [1,3‐dioxolane (DXL) and 1,3‐dioxepane (DXP)] and allows the preparation of dihydroxylated homopolymers as well as that of triblock copolymers. It was nevertheless shown that transacetalization leads to complications at the onset of the reaction. In order to shed some light on the reactions involved, we used a monoalcohol ‐ methanol ‐ instead of a diol. The products were separated and characterized: a monoadduct (methanol‐DXL) was observed, confirming the occurence of the active monomer mechanism, but dimethoxymethane was also observed, evidence of transacetalization between methanol and DXL. It was shown that fast equilibration takes place between the following compounds: (methanol + DXL), (monoadduct of methanol and DXL), (dimethoxymethane + ethyleneglycol). When p‐isopropenylbenzyl alcohol was used, it was possible to prepare macromonomers, i.e. poly(DXL) chains carrying polymerizable double bonds at their ends. Nevertheless because of the transacetalization reaction described above, a mixture of products was obtained.