Fast and Selective Main-Chain Scission of Vinyl Polymers Using the Domino Reaction in the Alternating Sequence for Transesterification.

Abstract

This communication reports on vinyl polymers capable of selective and fast main-chain scission (MCS). The trick is the domino reaction in an alternating sequence of methyl 2-(trimethylsiloxymethyl)acrylate and 5,6-benzo-2-methylene-1,3-dioxepane, a cyclic ketene acetal for radical ring-opening polymerization. Removal of the trimethylsilyl group using Bu4N+·F- readily led to MCS via irreversible transesterification of the ester backbone, affording a five-membered lactone fragment. The molar mass decreased drastically within 5 min, and no side reactions were observed. Control experiments suggest that the formation of a five-membered ring via a domino reaction is critical for fast and selective MCS. The terpolymers with methyl methacrylate and styrene also exhibited a large decrease in molar mass within 5 min. In addition, MCS was also observed for the heterogeneous reaction system in acidic aqueous media; treatment of the binary copolymer in a 50 wt % acetic acid solution resulted in a significant decrease in molar mass after 30 min. These results suggest efficient construction of degradable sites using a binary monomer system corresponding to the pendant trigger and ester backbone. Because this molecular design using a binary monomer system provides selective and fast MCS for terpolymers containing other vinyl monomers, it can provide various degradable vinyl polymers.