Synthesis of PMMA-PTHF-PMMA and PMMA-PTHF-PST linear and star block copolymers

Combination of cationic, redox free radical, and thermal free radical polymerizations was performed to obtain linear and star polytetramethylene oxide (poly-THF)-polymethyl methacrylate (PMMA)/polystyrene (PSt) multiblock copolymers. Cationic polymerization of THF was initiated by the mixture of AgSbF6 and bis(4,4' bromo-methyl benzoyl) peroxide (BBP) or bis (3,5,3',5' dibromom-ethyl benzoyl) peroxide (BDBP) at 20°C to obtain linear and star poly-THF initiators with MW varying from 7,500 to 59,000 Da. Poly-THF samples with hydroxyl ends were used in the methyl methacrylate (MMA) polymerization in the presence of Ce(IV) salt at 40°C to obtain poly(THF-b-MMA) block copolymers containing the peroxide group in the middle. Poly(MMA-b-THF) linear and star block copolymers having the peroxide group in the chain were used in the polymerization of methyl methacrylate (MMA) and styrene (St) at 80°C to obtain PMMA-b-PTHF-b-PMMA and PMMA-b-PTHF-PSt linear and star multiblock copolymers. Polymers obtained were characterizated by GPC, FT-IR, DSC, TGA, 1H-NMR, and 13C-NMR techniques and the fractional precipitation method. © 2004 Wiley Periodicals, Inc