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

摘要

The reaction of poly(methyl methacrylate) (PMMA), poly(i-butyl methacrylate), poly(2-hydroxyethyl methacrylate), and polymethacrylonitrile bearing organotellurium, organostibine, and organobismuthine co-living polymer end groups with 2,2,6,6-tetramethylpiperidine 1-oxy (TEMPO) under thermal or photochemical conditions gave the corresponding ω-vinylidene functionalized polymethacryiates and polymethacrylonitrile with high end group fidelity. Treatment of the PMMA with ethyl 2-[(tributylstannyl)methyl]acrylate also gave a PMMA bearing the same co-vinylidene end functionality. ~1H NMR, GPC, MALDITOF 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 co-polymer end structure.