In this study, we investigated dual radical and cationic controlled/living copolymerization of vinyl ether (VE) with acrylates in the presence of a Lewis acid and radical generator including thermal azo-initiator and photoradical initiator. In this system, a vinyl ether-type trithiocarbonate was employed as a RAFT reagent to control both radical and cationic polymerizations. The alternating radical RAFT copolymerization proceeded without the cationic homopolymerization of IBVE in the presence of weak and bulky aluminum Lewis acid, whereas interconvertible controlled/living copolymerization via dual radical and cationic species was induced using a strong Lewis acid such as metal halides to generate various comonomer sequence distributions, such as partitioned multiblock and tapered block copolymers, depending on the loading concentration of the Lewis acid. More importantly, photo-irradiation allows the interconvertible copolymerization switchable between the dual active species through the on-off experiment, which resulted in the introduction of functional groups at any point during the controlled/living copolymerization. The dual cationic and radical copolymerization process was also amenable to the other combination of the monomers, such as vinyl esters.

Photoswitchable dual radical and cationic controlled/living polymerization for various comonomer sequence distributions

254th National Meeting (2017)

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