Synthesis of novel fluorinated polymers: Facile carbon-carbon bond formation aided by fluorine substituents

Abstract

The review article summarizes my work as a macromolecular synthetic chemist to leave it on the sands of time. Fluorinated vinyl compounds with high addition reactivities toward anionic and radical species were demonstrated to allow facile preparation of fluorinated polymers. Novel anionic addition polymerization of fluorinated vinyl monomers, which generally show poor homopolymerization reactivities under radical conditions, has been developed. Measurement of pseudo first-order rate constants, k′, demonstrated the order of reactivity of 18 fluorinated acrylates and methacrylates by the reaction with diethyl(ethyl cyanoacetato)aluminum. The new field, anionic polyaddition, was accomplished by the double Michael addition of bis(2-trifluoromethylacrylate)s to active methylene compounds. Radical addition reaction of several fluorinated vinyl compounds with organic compounds possessing carbon-hydrogen bonds afforded fluorinated organic compounds. By developing the novel radical addition, the polyaddition reaction was achieved to incorporate fluorinated vinyl monomers into polymer main chains with organic compounds possessing carbon-hydrogen bonds, the first use for these polymers as starting materials of macromolecular syntheses. Facile carbon-carbon bond formation reactions were made possible with the aid of fluorine substituents under anionic and radical conditions. These reactions were then developed into the formation of the carbon-carbon bond from a carbon-hydrogen bond as a functional group in aliphatic compounds. © The Society of Polymer Science, Japan (SPSJ). All rights reserved.