EPR studies on regio-selective H-abstraction by “magic blue” reagent from polymers

The radical reactions of polyolefin and olefin copolymers (4–9), polydienes and diene coplymers (10–15), and polysiloxane (16) with “magic blue” reagent containing H-abstracting agent-bis{perfluoro-1-[1-(2-fluorosulfonyl)ethoxy]ethyl}nitroxide [FSO2CF2CF2OCF(CF3)]2N(O) (2)and spin trap-perfluoro-1-nitroso-[1-(2-fluoro-sulfonyl)ethoxy]ethane FSO2CF2CF2OCF(CF3)NO (3) were studied by EPR detection of the spin adducts of the corresponding polymeric radicals generated in the H-abstraction step to the spin trap 3, namely, the nitroxides FSO2CF2CF2OCF(CF3)N(O) (polymer-H) 17–29. EPR studies have provided information about the regio-selectivity of H-abstraction, the subsequent radical steps followed H-abstraction and grounded a possibility of employing “magic blue” reagent in polymer modification via H-abstraction-initiated grafting polymerization.

Graphical abstractThe generation of polymer nitroxides 17–29 via H-abstraction/spin trapping reactions by new “magic blue” (2 + 3) from a series of polymers 4–16 are reported. Figure optionsDownload full-size imageDownload as PowerPoint slide