Well-defined phosphonate-functional copolymers through RAFT copolymerization of dimethyl-p-vinylbenzylphosphonate

Dibenzyltrithiocarbonate-mediated RAFT polymer- ization of dimethyl-p-vinylbenzylphosphonate and its copoly- merization with styrene are studied in order to access well- defined statistical and block copolymers containing controlled amounts of dimethylphosphonate groups. NMR and SEC anal- ysis of the (co)polymers confirm the controlled character of the polymerizations. ABA triblock copolymers are treated with TMSiBr/MeOH in order to transform the dimethylphosphonate groups into phosphonic acids while keeping the midchain tri- thiocarbonate group and triblock nature unaffected. Alterna- tively, the combination of trithiocarbonate aminolysis with TMSiBr/MeOH treatment of the same triblock copolymers leads to phosphonic acid-functional diblock copolymer counterparts. V C 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 00, 000-000