Hydrogen-Transfer Polymerization of Vinyl Monomers Derived from p-Tolylsulfonyl Isocyanate and Acrylamide Derivatives

Article abstract of DOI:10.1246/bcsj.71.1137

The hydrogen-transfer polymerization of N-acryloyl-N′-p-tolylsulfonylurea (1) prepared by the reaction of p-Molylsulfonyl isocyanate with acrylamide, was carried out at 80°C for 24 h in N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile (MeCN), and toluene containing N-phenyl-2-naphthylamine (1 mol%) as a radical inhibitor using t-BuOK or 1,3-diazabicyclo[5.4.0]undec-7-ene (DBU) (3 mol%) as an initiator. Polymers obtained by t-BuOK in polar solvents were composed of the hydrogen-transfer polymerization unit selectively, while those afforded by t-BuOK in less polar solvents or by DBU were composed of both the hydrogen-transfer and the vinyl polymerization units. Although Naciyloyl-N-methyl-N′-p-tolylsulfonylurea (2) prepared by the reaction of p-tolylsulfonyl isocyanate with N-methylacrylamide, gave low molecular-weight compounds (6-8) via the generation of the sulfonyl isocyanate, N-acryloyl-N′-methylN′-p-tolylsulfonylurea (3) underwent the selective hydrogen-transfer polymerization.