Synthesis and Characterization of End-Linked Amphiphilic Copolymer Conetworks Based on a Novel Bifunctional Cleavable Chain Transfer Agent

A novel bifunctional bis(hemiacetal ester) chain transfer agent (CTA), 1,2-bis[1-(4-cyano-4-methyl-1-oxo-4-(phenylcarbonothioylthio)butanoxy)ethoxy]ethane (CMPTBEE), appropriate for the reversible addition fragmentation chain transfer (RAFT) polymerization of methacrylate monomers, was successfully synthesized and used for the preparation of a family of 10 hydrolyzable end-linked polymer (co)networks. The family comprised three methyl methacrylate (MMA) homopolymer networks with different degrees of polymerization, 100, 150, and 200, and seven end-linked amphiphilic polymer conetworks of MMA and 2-(dimethylamino)ethyl methacrylate (DMAEMA) with a constant overall degree of polymerization equal to 200 but various compositions and architectures. The agreement of the experimentally measured molecular weights with the theoretically expected ones and the low molecular weight dispersities of the linear precursors to the (co)networks indicated successful control of the polymerization. All (co)networks were characterized in terms of their sol fraction and in terms of their degree of swelling in THF. The value of the former was found in the range between 4 and 50%, whereas that of the latter was around 13%. The presence of the hemiacetal ester groups allowed the hydrolysis of the most hydrophilic, DMAEMA-rich conetworks. The resistance to hydrolysis of the other (co)networks could be attributed to the large hydrophobic blocks surrounding and protecting from hydrolysis the hemiacetal ester groups of the CTA residue in the conetworks.