TY - JOUR A1 - Britner, Judita A1 - Ritter, Helmut T1 - Methylenelactide: vinyl polymerization and spatial reactivity effects JF - Beilstein Journal of Organic Chemistry PY - 2016/// VL - 12 SP - 2378 EP - 2389 SN - 1860-5397 DO - 10.3762/bjoc.12.232 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.12.232 KW - copolymerization KW - kinetic study of the radical homopolymerization KW - push–pull monomer KW - reversible addition fragmentation chain transfer (RAFT) N2 - The first detailed study on free-radical polymerization, copolymerization and controlled radical polymerization of the cyclic push–pull-type monomer methylenelactide in comparison to the non-cyclic monomer α-acetoxyacrylate is described. The experimental results revealed that methylenelactide undergoes a self-initiated polymerization. The copolymerization parameters of methylenelactide and styrene as well as methyl methacrylate were determined. To predict the copolymerization behavior with other classes of monomers, Q and e values were calculated. Further, reversible addition fragmentation chain transfer (RAFT)-controlled homopolymerization of methylenelactide and copolymerization with N,N-dimethylacrylamide was performed at 70 °C in 1,4-dioxane using AIBN as initiator and 2-(((ethylthio)carbonothioyl)thio)-2-methylpropanoic acid as a transfer agent. ER -