Well-defined polystyrenes were successfully prepared by the CuX/(dN)bpy or CuX/ PMDETA catalyzed atom transfer radical polymerization of styrene using 1-phenylethyl bromide (1-PEBr) or benzyl bromide (BnBr) as initiators. We found that the CuX/PMDETA catalyzed ATRP of styrene proceeded faster than CuX/(dN)bpy catalyzed counterpart in bulk, diphenyl ether (DPE) and anisole. Using CuX/(dN)bpy catalyst, well-defined polystyrenes were obtained with good chain-end functionalities and low polydispersity (Mw/Mn <1.5) compared to CuX/PMDETA catalyst. The CuBr/PMDETA catalyzed ATRP of n-butyl acrylate (nBA), n-butyl methacrylate (nBMA), and tert-butyl methacrylate (tBMA) were also proceeded in a controlled manner. The molecular structure and molecular weight of polymers were determined by proton nuclear magnetic resonance (1H NMR) spectroscopy and size exclusion chromatography (SEC), respectively.

Well-defined functional poly( p -phenyl styrenesulfonate) and poly( p -phenyl styrene-sulfonate- co -styrene) were successfully synthesized by the atom transfer radical polymerization (ATRP) using CuBr/bpy(PMDETA) catalyst and 1-phenylethyl bromide (1-PEBr) as an ATRP initiator in diphenyl ether (DPE) or dimethyl formamide (DMF). In both homo- and copolymers, the CuBr/PMDETA catalytic system in DPE or DME showed higher yield than CuBr/bpy and the polydispersity index (PDI) of polymer was low. Using PMDETA or bpy as a ligand in DMF, the high yield with high PDI was obtained than in DPE. We found that the CuBr/PMDETA catalyzed ATRP of p -phenyl styrenesulfonate and copolymerization with styrene comonomer in DPE proceeded in a controlled manner. The polymers containing sulfonic acid were obtained by the chemical deprotection of protecting group, followed by acidification. The molecular structure, molecular weights and thermal properties of the copolymers were determined by nuclear magnetic resonance ( 1 H NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, size exclusion chromatography (SEC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively.