RAFT Polymerization of 2‐(tert‐Butoxycarbonyloxy)Ethyl Methacrylate and Transformation to Functional Polymers via Deprotection and the Subsequent Polymer Reactions

Abstract

Reversible addition–fragmentation chain transfer (RAFT) polymerization of 2‐(tert‐butoxycarbonyloxy)ethyl methacrylate (BHEMA) is carried out using 4‐cyano‐4‐((dodecylsulfanylthiocarbonyl)sulfanyl)pentanoic acid as the RAFT agent. The polymers with a controlled molecular weight and polydispersity are produced when a large amount of the RAFT agent is used. The RAFT polymerization of isobutyl methacrylate is also carried out using poly(2‐(tert‐butoxycarbonyloxy)ethyl methacrylate) (PBHEMA) as the macro‐RAFT agent in order to synthesize diblock copolymers with a narrow molecular weight distribution. It is revealed that the control of the polymerization of BHEMA is achieved under limited polymerization conditions. Then, the acid‐catalyzed deprotection of tert‐butoxycarbonyloxy groups of PBHEMA is performed in the presence of trifluoroacetic acid at room temperature to obtain polymers with a hydroxy group in the side chain. The hydroxy‐containing polymers are further reacted with 2‐isocyanatoethyl acrylate and methacrylate to synthesize precursor polymers used for a thermally curing system.