文摘
Poly(styrene-alt-maleic anhydride)-block-poly(methacrylate-ran-styrene) block copolymers were synthesized from low dispersity (Mw/Mn=1.24) and perfectly alternating poly(styrene-alt-maleic anhydride) macroinitiators, by nitroxide mediated controlled radical polymerization (NMP), using various methacrylate-rich mixtures: methyl methacrylate/styrene (MMA/S), ethyl methacrylate/styrene (EMMA/S), n-butyl methacrylate/styrene (BMA/S) and benzyl methacrylate/styrene (BzMA/S). Some irreversible termination was present during the chain extension from the macroinitiator, resulting in some bimodality in the molecular weight distribution of the final block copolymer (≈2% to ≈25% dead chains) which is common for methacrylate/styrene copolymerizations by NMP. The resulting final block copolymers were determined to be methacrylate-rich (molar ratio XMA/S ≈3.3 to 5.5) by 1H NMR and the resulting glass transition temperature (Tg) of the chain-extended segments were found to be similar to the coresponding pure poly(methacrylate)s. NMP allows the controlled placement of functional maleic anhydride containing segments within a block copolymer with tunable mechanical properties by simple substitution of methacrylate monomer used in synthesis.