The preparation of α-bis and α,ω-tetrakis aromatic oxazolyl- and carboxyl-functionalized polymers using 1,1-bis[4-(2-(4,4-dimethyl-1,3-oxazolyl))phenyl]ethylene in atom transfer radical polymerization reactions

© 2014 Society of Chemical Industry. The synthesis of a new symmetrically disubstituted 1,1-diphenylethylene derivative, 1,1-bis[4-(2-(4,4-dimethyl-1,3-oxazolyl))phenyl]ethylene, and its use in the preparation of α-bis(oxazolyl), α,ω-tetrakis(oxazolyl), α-bis(carboxyl) and α,ω-tetrakis(carboxyl) polystyrene derivatives by atom transfer radical polymerization methods are reported. The preparation of new compounds, 1,1-bis[4-(2-(4,4-dimethyl-1,3-oxazolyl))phenyl]ethanol and a new symmetrically disubstituted 1,1-diphenylethylene derivative, 1,1-bis[4-(2-(4,4-dimethyl-1,3-oxazolyl))phenyl]ethylene, is described. 1,1-Bis[4-(2-(4,4-dimethyl-1,3-oxazolyl))phenyl]ethylene was utilized as a dioxazolyl initiator precursor for the polymerization of styrene by atom transfer radical polymerization (ATRP) methods to produce α-bis(oxazolyl) polystyrene. The kinetic study of the polymerization process indicated that the free radical polymerization reaction for the preparation of α-bis(oxazolyl) polystyrene follows first-order rate kinetics with respect to monomer consumption. α,ω-Tetrakis(oxazolyl) polystyrene was prepared by a new, in situ, controlled/living, post-ATRP chain-end-functionalization reaction which involves the direct addition of 1,1-bis[4-(2-(4,4-dimethyl-1,3-oxazolyl))phenyl]ethylene to the ω-terminus of the α-bis(oxazolyl) polystyrene derivative, without the isolation and purification of the polymeric precursor. α-Bis(carboxyl) and α,ω-tetrakis(carboxyl) polystyrene derivatives were obtained by the quantitative chemical transformation of the oxazoline groups of the respective aromatic oxazolyl chain-end-functionalized polystyrene derivatives to the aromatic carboxyl groups. The organic precursor compounds, the dioxazolyl-functionalized 1,1-diphenylethylene derivative and the functionalized polymers were characterized using 1H NMR and 13C NMR spectrometry and Fourier transform infrared spectroscopy, size-exclusion and thin-layer chromatography and non-aqueous titration measurements.