Influence of Initiator's Chemical Composition On the Thermal Stability of Poly(styrene)-b-Poly(2,2,3,4,4,4-hexafluorobutyl-methacrylate) Synthesized Using Atom Transfer Radical Polymerization

Novel fluoroblock copolymers based on poly(styrene) (PS), poly(2,2,3,4,4,4-hexafluorobutyl- methacrylate) (HEMA) and 2-(perfluoroalkyl)ethanol were synthesized using Atom Transfer Radical Polymerization  (ATRP) and  characterized by thermogravimetrical analysis.  These block copolymers were synthesized employing two different initiators:  a fluoro-macroinitiator obtained by the esterification of 2-(perfluoroalkyl)ethanol (Zonyl®) and (1-bromoethyl) benzene. The resulting block copolymers were characterized using several techniques: Gel permeation chromatography (GPC), Nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Significant differences in their properties were observed for the different block copolymers suggesting that the initiator chemical composition can have a profound effect in the chemistry and morphology of the resulting block copolymers.