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JOURNAL ARTICLE
RESEARCH SUPPORT, U.S. GOV'T, NON-P.H.S.
Polymer Valence Isomerism: Poly(Dewar- o-xylylene)s.
Journal of the American Chemical Society 2018 April 19
Poly( o-xylylene) (POX) has long been a challenging synthetic target despite its simple structure and potentially useful physical properties. In this report, we demonstrate a valence isomer strategy that leads to the formation of high molecular weight POX via an intermediate polymer of a unique structure, namely poly(Dewar- o-xylylene) (PDOX). We show that the free radical polymerization of highly strained Dewar- o-xylylene (DOX) monomer afforded PDOX, a material with a high density of Dewar benzene units in the backbone through ring-retaining propagation. The thermal- and photoinduced isomerizations of PDOX to produce POX were investigated. This chemistry yields POXs that are difficult to obtain using traditional methods. Moreover, it also provides a potential entry into new reconfigurable materials featuring highly efficient postpolymerization main chain structural transformations.
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