Synthesis of structurally well-controlled ω-vinylidene functionalized poly(alkyl methacrylate)s and polymethacrylonitrile by organotellurium, organostibine, and organobismuthine-mediated living radical polymerizations

The reaction of poly(methyl methacrylate) (PMMA), poly(i-butyl methacrylate), poly(2-hydroxyethyl methacrylate), and polymethacrylonitrile bearing organotellurium, organostibine, and organobismuthine ω-living polymer end groups with 2,2,6,6-tetramethylpiperidine 1-oxy (TEMPO) under thermal or photochemical conditions gave the corresponding ω-vinylidene functionalized polymethacrylates and polymethacrylonitrile with high end group fidelity. Treatment of the PMMA with ethyl 2-[(tributylstannyl)methyl]acrylate also gave a PMMA bearing the same ω-vinylidene end functionality. 1H NMR, GPC, MALDI TOF MS, and thermogravimetric analyses revealed the highly controlled and defined structure of poly(alkyl methacrylate)s and polymethacrylonitrile in terms of molecular weight, molecular weight distribution, and the ω-polymer end structure.