Surface modification of halogenated polymers. 10. Redox catalysis induction of the polymerization of vinylic monomers. Application to the localized graft copolymerization of poly(tetrafluoroethylene) surfaces by vinylic monomers

The polymerization of vinylic monomers such as DMAEMA ( 2-dimethyaminoethyl methacrylate) can be triggered electrochemically by an electrode and/or a solution electrogenerated reducer ( redox catalysis). The electrochemical mechanism is similar to that of other vinylic monomers. As the polymerization can be induced by redox catalysis, the DMAEMA polymerization can be transposed onto the n-doped poly( tetrafluoroethylene) ( PTFE) surfaces obtained by local scanning electrochemical microscopy reduction of PTFE. The copolymerization is evidenced by the ion-exchange properties of the obtained material. The amount of deposited polymeric material, of estimated width 50-150 nm, is related to the different experimental conditions. The mechanistic observations about the DMAEMA reduction allow a better insight into the PTFE reduction and subsequent DMAEMA copolymerization. It also nicely demonstrates that higher current densities are supported by microelectrode edges.