Organocatalytic Group Transfer Polymerization of N,N-Diethylsorbamide Leading to trans-1,4-Addition Polymer: Controlled/Living Nature Applied to the One-Pot Synthesis of Block Copolymer with Poly(N,N-dimethylacrylamide)

A sorbic acid derivative in the form of acid amide, such as N,N-diethylsorbamide (DESAm), has been added to a repertoire of the group transfer polymerization (GTP) method using silyl ketene acetal (SKA) as an initiator. Systems with the organic acids of Me3SiNTf2 in dichloromethane and/or the organic superbase t-Bu-P4 in toluene can afford poly(DESAm). The GTP tendency of DESAm was investigated and compared with that of a simple vinylacrylamide monomer such as N,N-dimethylacrylamide (DMAm). A significant difference in the polymerization activities of DESAm and DMAm was revealed, which enabled the development of an advanced system for the synthesis of block copolymers. The random one-pot GT copolymerization (GTcoP) of DESAm (A unit) and DMAm (B unit) with SKAMe using t-Bu-P4 afforded a BA-diblock copolymer. A series of block copolymer architectures were similarly prepared including ABA-, BAB-, and BABA-block copolymers.